DIBORON-MEDIATED REDUCTIVE COUPLING OF IMINES: DIVERGENT DIASTEREOCONTROL AND ACTIVATION OF TETRAALKOXYDIBORONS By Ryan M. Fornwald A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of Chemistry – Doctor of Philosophy 2021 i ABSTRACT DIBORON-MEDIATED REDUCTIVE COUPLING OF IMINES: DIVERGENT DIASTEREOCONTROL AND ACTIVATION OF TETRAALKOXYDIBORONS By Ryan M. Fornwald Diborons are a paradox: despite featuring a highly electron deficient boron-boron bond, they are powerful reducers. The steric and electronic properties of their substituents have an enormous influence on the reactivity of the boron-boron bond, offering the potential to control diastereoselectivity, regioselectivity, chemoselectivity, and absolute stereochemistry of diboron-mediated reactions. Recently, N-borylpyridinyl radicals were reported to form via homolytic cleavage of dicoordinate bis-pyridine-diboron complexes. These species reductively dearomatize pyrazines, aromatize p-quinones, and deoxygenate sulfoxides. Additionally, they undergo dimerization reactions that suffer from poor regioselectivity and diastereoselectivity. However, more recently, dicoordinate bis-isoquinoline-diboron complexes were reported to undergo highly diastereoselective carbon-carbon bond forming [3,3]-sigmatropic rearrangements. Impressively, this work was expanded to include enantioselective reductive imine couplings. However, these reactions can only selectively access thermodynamic diastereomers, and a preference for kinetic diastereomers has never been reported. This limitation extends to all reductive imine coupling reactions that use different reagents, conditions, or mechanisms. We sought to develop reactions that would overcome this limitation, and to understand the factors that influence diastereoselectivity in diboron-mediated reductive coupling reactions of imines. We found that varying the steric and electronic properties of ii the diolate ligands on the diboron, and the solvent, enabled the stereodivergent synthesis of all diastereomers of 2,3-diaryltetrahydroquinoxalines. Additionally, we developed unique conditions for the activation of tetraalkoxydiborons, resulting in greatly increased reactivity and kinetic diastereoselectivity. We then explored the mechanism of these reactions computationally to aid in our understanding of how to proceed with further optimization. Finally, we developed a simple, fast protocol for the synthesis of tetraalkoxydiborons and diboron diolates to enable us to rapidly explore the effects of the structure of the diboron on reactivity and selectivity. iii Copyright by RYAN M. FORNWALD 2021 iv For my grandfather, who returned my mother from panic while I erased my innocence with confident claims that the gas evolved from a pile of nails deposited in hydrogen peroxide would inflate a thermonuclear Hindenberg for which Ivy Mike was no rival. However, our home survived its whimpers, and my career in chemistry continued. Inadvisably. v ACKNOWLEDGMENTS First, I would like to acknowledge my advisor, Mitch Smith, for supporting my love for chemistry, encouraging creativity, and giving me a great deal of freedom to pursue my own ideas. The most important thing to me in grad school was freedom, and I am thankful to have spent my Ph.D. working on chemistry that truly excites me. I also wish to thank the members of my committee (Dr. Robert E. Maleczka, Jr., Dr. Babak Borhan, Dr. Aaron Odom, and Dr. John Frost) for their advice and guidance. I thank Dr. Melanie Sanford (University of Michigan) for giving me my first opportunity to work in a research lab, and Dr. John Wolfe, who sparked my ever-lasting love for organic chemistry. My experiences at UM are why I knew graduate school is what I needed to do next in my life. My thanks also go out to my labmates in the Smith and Maleczka groups for their friendship – especially for the conversations with Tim (about hypercanes), conversations with Cash (about ergospheres), adventurous bowling trips with Alex, and for Yu-Ling, who is greatly missed. I give thanks to my family: my parents, who tolerated my ill-advised science experiments at a young age (without their relentless and unwavering support, there is no way I would’ve lived long enough to make it into a Ph.D. program); and my sister Natalie, who makes me laugh at all hours of the day. Finally, I acknowledge (a) my partner, Dr. Maris Cinelli, for being incredibly supportive throughout my graduate school experience, I look forward to our lifetime together in chemistry and otherwise; and (b) our favorite little kitty-cat, Nitro, who never failed to extend his claws to remind me that he still existed while I wrote this thesis. vi TABLE OF CONTENTS LIST OF TABLES ........................................................................................................... ix LIST OF FIGURES .......................................................................................................... x LIST OF SCHEMES ....................................................................................................... xi KEY TO ABBREVIATIONS ....................................................................................... xiii Chapter 1. Introduction to the Chemistry of Diborons and Vicinal Diamines ........... 1 Ionic Reactions................................................................................................................ 3 Radical Reactions............................................................................................................ 5 Sigmatropic Reactions .................................................................................................... 9 REFERENCES ............................................................................................................. 15 Chapter 2. Diboron-Mediated Stereodivergent Synthesis of All Diastereomers of 2,3- Diaryltetrahydroquinoxalines via Reductive Cyclization of Diimines ...................... 21 Introduction ................................................................................................................... 21 Discussion of a Potential Mechanism ........................................................................... 23 Conclusions ................................................................................................................... 28 Experimental Section .................................................................................................... 29 APPENDIX ................................................................................................................... 33 REFERENCES ............................................................................................................. 42 Chapter 3. Activation of Tetraalkoxydiborons by B2O3: Scope and Reactivity ....... 46 Introduction ................................................................................................................... 46 Scope of the Diboron and Additives ............................................................................. 46 Scope of the Imine Substrate ........................................................................................ 49 Conclusions ................................................................................................................... 56 Experimental Section .................................................................................................... 57 APPENDICES .............................................................................................................. 66 APPENDIX A: Spectral Data.................................................................................... 67 APPENDIX B: GC-MS Results for Table 3.1 .......................................................... 99 APPENDIX C: Computational Coordinates ........................................................... 106 REFERENCES ........................................................................................................... 114 Chapter 4. Probing the Origins of Diastereoselectivity Using Computational Models and New Experimental Conditions ............................................................................. 118 Introduction ................................................................................................................. 118 Investigation of the Sigmatropic Mechanism ............................................................. 120 Investigation of the Ionic Mechanism ......................................................................... 129 Conclusions ................................................................................................................. 132 Experimental Section .................................................................................................. 137 APPENDICES ............................................................................................................ 139 vii APPENDIX A: Bond Distances .............................................................................. 140 APPENDIX B: Computational Coordinates ........................................................... 141 REFERENCES ........................................................................................................... 361 Chapter 5. An Improved Preparation of Tetraalkoxydiborons and Diboron Diolates from Tetrahydroxydiboron .......................................................................................... 364 Introduction ................................................................................................................. 364 Scope of the Reaction ................................................................................................. 367 Conclusions ................................................................................................................. 369 Experimental Section .................................................................................................. 369 APPENDIX ................................................................................................................. 376 REFERENCES ........................................................................................................... 407 viii LIST OF TABLES Table 3.1. Screen of diborons and additives for reductive coupling of imine 3 .............. 47 Table 3.2. Scope of imine coupling partners .................................................................... 50 Table 4.1. Calculated energies (G) ............................................................................... 126 Table 4.2. Dipole moments ............................................................................................. 126 Table 4.3. Calculated transition state energies (G‡) ..................................................... 128 Table 4.4. Bond distance change from intermediate complex to transition state (Å) ..... 140 Table 4.5. B-B bond distances (Å).................................................................................. 140 Table 4.6. C-C bond distances (Å).................................................................................. 140 Table 5.1. Scope of the reaction: diboron diolates (32-39) prepared from 30 ................ 368 ix LIST OF FIGURES Figure 1.1. Relative stability and reactivity of various common diborons ......................... 2 Figure 1.2. Significant molecules containing the vicinal diamine motif .......................... 12 Figure 4.1. Dipole moments of representative examples of substrates, intermediate complexes, transition states, and products ...................................................................... 122 Figure 4.2. Concerted [3,3]-sigmatropic rearrangement transition states ....................... 127 Figure 4.3. Structure of B2hmp2...................................................................................... 129 Figure 4.4. Generalized reaction coordinates for reactions in DMF and benzene for products 2b and 2c (relative energies given in kcal/mol) ............................................... 133 x LIST OF SCHEMES Scheme 1.1. Several metal-catalyzed reactions of diborons ............................................... 2 Scheme 1.2. Examples of three fundamental ionic diboron reaction types ........................ 4 Scheme 1.3. Postulated single-electron reductants in reactions with diborons, base, and pyridines.............................................................................................................................. 5 Scheme 1.4. Captodative stabilization vs. spin delocalization in N-borylpyridinyl radicals ... 6 Scheme 1.5. Racemization of organoboranes induced by nucleophiles ............................. 7 Scheme 1.6. Reactions of N-borylpyridinyl radicals .......................................................... 7 Scheme 1.7. N-Borylpyridinyl radicals and reversible dimerization via radical recombination ..................................................................................................................... 8 Scheme 1.8. Concerted [3,3]-sigmatropic reaction mechanism from a diboron complex .... 9 Scheme 1.9. Diboron-mediated reductive couplings of imines ........................................ 10 Scheme 1.10. Reductive couplings of isoquinolines with (a) diborons vs. (b) metals ..... 10 Scheme 1.11. Reductive coupling transition state from a B2pin2•2(isoquinoline) complex .... 11 Scheme 1.12. A metal-mediated aza-pinacol coupling ..................................................... 13 Scheme 2.1. Imine and isoquinoline reductive couplings related to this work................. 22 Scheme 2.2. Reductive [3,3]-sigmatropic rearrangement of a diimine-diboron complex...... 23 Scheme 2.3 Proposed mechanism for formation of 2a and heterolytic cleavage of pyridine diboron alkoxide complexes ............................................................................... 24 Scheme 2.4. Reaction conditions for diastereoselective synthesis of 2a-2c along with putative transition states corresponding to the formation of each major isomer via a [3,3]- sigmatropic pathway ......................................................................................................... 26 Scheme 2.5. E/Z Isomerization of imines in the presence of boroxines ........................... 27 Scheme 2.6. Role of A1,3 strain in controlling diastereoselectivity in Scheme 2.2........... 28 Scheme 3.1. Wet B2(OH)4 as an aromaticity-breaking reductant ..................................... 47 Scheme 3.2. Equilibrium between B2(OH)4 and its anhydride ......................................... 48 xi Scheme 3.3. Construction of piperazines, I ...................................................................... 51 Scheme 3.4. Construction of piperazines, II ..................................................................... 52 Scheme 3.5. Construction of 1,4-diazepanes by diboron-mediated reductive coupling of imines ................................................................................................................................ 53 Scheme 3.6. Reported formation of trimethoxyboroxine ................................................. 53 Scheme 3.7. Reaction of B2(OMe)4 with B2O3: insertion vs. metathesis ......................... 54 Scheme 3.8. Prior reports of bis-pyrodiborate structures and analogs ............................. 54 Scheme 3.9. Reaction of B2(OMe)4 with TFAA............................................................... 55 Scheme 3.10. Relative energies of bis-pyrodiborates and analogs ................................... 56 Scheme 4.1. Concerted [3,3]-sigmatropic rearrangement mechanism (a) and proposed transition states (b) as discussed in Chapter 2 ................................................................ 118 Scheme 4.2. (a) Proposed ionic mechanism and transition state and (b) literature precedent ......................................................................................................................... 120 Scheme 4.3. Isomerization of 1,1-B2cat2 into 1,2-B2cat2. ............................................... 121 Scheme 4.4. Reductive coupling of 1 with added base and catechol ............................. 130 Scheme 4.5. Modeling the ionic mechanism .................................................................. 132 Scheme 5.1. Previously reported syntheses of diboron diolates and similar compounds ... 365 Scheme 5.2. This work.................................................................................................... 366 Scheme 5.3. Synthesis of tetramethoxydiboron (31) ...................................................... 368 xii KEY TO ABBREVIATIONS 4-tBu-cat 4-tert-Butylcatecholato AcCl Acetyl chloride All Allyl B-B Boron-boron bond B(OMe)3 Trimethyl borate B2cat2 Bis(catecholato)diboron B2eg2 Bis(ethyleneglycolato)diboron B2pin2 Bis(pinacolato)diboron B2(NMe2)4 Tetrakis(dimethylamino)diboron B2(OEt)4 Tetraethoxydiboron B2(OMe)4 Tetramethoxydiboron B3O3(OMe)3 Trimethoxyboroxine Bn Benzyl C-C Carbon-carbon bond cPr Cyclopropyl cat Catecholato CDCl3 Deuterated chloroform CD3CN Deuterated acetonitrile CH(OEt)3 Triethyl orthoformate CH(OMe)3 Trimethyl orthoformate cod 1,5-Cyclooctadiene d Doublet (NMR) xiii dan 1,8-Diaminonaphthalene dba Dibenzylideneacetone DCM Dichloromethane DMF N,N-Dimethylformamide DFT Density Functional Theory dtbpy 4,4'-Di-tert-butyl-2,2'-bipyridine eg Ethylene glycolate or glycolato Et Ethyl EtO Ethoxyl Et2O Diethyl ether Et3N Triethylamine Equiv Equivalents GC-MS Gas Chromatography-Mass Spectrometry HCl Hydrochloric acid hmp o-2-(Hydroxymethyl)phenylato Hz Hertz iPr Isopropyl kcal Kilocalorie m Multiplet (NMR) M Molar (concentration) Me Methyl MeCN Acetonitrile MeO Methoxyl xiv MeOH Methanol MHz Megahertz mol Mole mp Melting point nPr n-Propyl neop Neopentylglycolate NMR Nuclear magnetic resonance o-Tol ortho-Tolyl Ph Phenyl pin Pinacolato PPh3 Triphenylphosphine PTFE Polytetrafluoroethylene rt Room temperature THF Tetrahydrofuran TFA Trifluoroacetic acid TFAA Trifluoroacetic anhydride s Singlet (NMR) SMD Solvent Model based on Density t Triplet (NMR) tBu tert-Butyl xv Chapter 1. Introduction to the Chemistry of Diborons and Vicinal Diamines Although diborons (Y2BII–BIIY2) possess a pair of adjacent, empty p-orbitals in their extremely electron deficient (and paradoxically, powerfully reducing) B-B bond, they can be stabilized via judicious choice of substituents to allow convenient use and for their reactivity to be controlled (Figure 1.1).1 Diborons with hydrogen or alkyl substituents are generally very unstable, and only sterically bulky tetraalkyldiborons have been characterized – for example, while B2Et42 has been synthesized, B2Me4 and B2H4 are unknown compounds. Halogen substituents can somewhat stabilize the B-B bond via π- donation, and B2F4, featuring excellent orbital overlap between boron and fluorine atoms, is stable at room temperature.3 Less favorable orbital overlap between boron and the other halogens results in diminished stability for B2Cl4 and B2Br4, which spontaneously disproportionate (in the absence of solvent) into boron trihalides and polyhedral boron halides (BX)n (X = Cl, Br) at room temperature.4 Nitrogen and oxygen are much stronger π-donors than the halogens, and so diborons with dialkylamino substituents are vastly more stable,5 and those derived from diolate ligands are even bench stable.1 Interest in the reactivity of diborons has increased dramatically in the last few decades, beginning with their use as reagents (boron donors) in metal-catalyzed transformations (Scheme 1.1), such as alkyne, allene, and alkene diborylations,8-10 Miyuara borylations,11 and C-H borylation of arenes.12-13 1 Figure 1.1. Relative stability and reactivity of various common diborons.1-7 Scheme 1.1. Several metal-catalyzed reactions of diborons.8-13 2 More recently, interest in metal-free transformations has surged. Many transition metal-catalyzed transformations have been replicated without metals, such as the aforementioned diborylation reactions, and a variety of related new transformations, such as diborations of alkenes.14 Critically, there are a few specific classes of metal-free reactions of diborons that have been explored in great depth that are relevant to the topic of this thesis: 1. Ionic reactions: Those catalyzed or mediated by strong nucleophiles (alkoxide bases, NHCs, and amines), sometimes employing pyridines as catalysts or substrates. 2. Non-photochemical radical reactions: Those catalyzed or mediated by pyridines, generating a reactive N-borylpyridinyl radical intermediate. 3. Sigmatropic reactions: Those that proceed through [3,3]-sigmatropic rearrangements of diboron complexes, such as those derived from allylic alcohols or imines – having closed transition states, they offer high levels of stereocontrol. Ionic Reactions. Ionic diboron reactions can be divided into three fundamental types (Scheme 1.2), where a diboron complex is either: (a) The reactive intermediate (Scheme 1.2a); or (b) a precursor to a reactive intermediate, generated by B-B bond heterolysis (Scheme 1.2b); or (c) a powerful single-electron reductant, or a precursor to a powerful single-electron reductant (Scheme 1.2c). 3 Scheme 1.2. Examples of three fundamental ionic diboron reaction types.a,15-17 a Three possible intermediates for reaction (c) are shown in Scheme 1.3 (highlighted in blue). Alkenes can be diborylated by diborons in the presence of a nucleophilic catalyst, such as alkoxide15 or amine18 bases (Scheme 1.2a). These reactions have been proposed to proceed directly from an anionic diboron-alkoxide or diboron-NHC complex.19 Chiral versions have been developed using B2neop2 (neop = neopentylglycolato) as the stoichiometric diboron source and a variety of chiral 1,2-diols as catalysts.20 Borylation of imines,21 and α,β-unsaturated carbonyl compounds,22-23 can also be accomplished by these complexes, and vinylepoxides and vinylaziridines undergo borylative ring opening.24 Studies into the nature of the reductant generated by the reaction of 4-phenylpyridine with KOMe and B2pin2 revealed that heterolysis of the B-B bond occurred to form a 4 dearomatized anionic complex – when treated with methanol, the 1,4-hydropyridine was generated (Scheme 1.2b).16 Aryl halides can be borylated in the presence of pyridines and alkoxide bases (effectively a metal-free Miyaura borylation)17 (Scheme 1.2c). While the nature of the reducing species is unclear25 (possibilities are shown in Scheme 1.3), single electron reduction of aryl halides occurs under these conditions. These aryl halide radical anions fragment to afford aryl radicals, which rapidly react with the diboron (or a diboron complex) to yield aryl boronic esters. Scheme 1.3. Postulated single-electron reductants in reactions with diborons, base, and pyridines.25 Radical Reactions. Naked boryl radicals themselves are exceedingly unstable due to their electron deficient nature.26 However, N-borylpyridinyl radicals are far more stable – not only is their electron deficiency greatly attenuated, but spin is also delocalized by the pyridine, 5 and 4-arylpyridines are able to further delocalize spin. Pyridines with electron withdrawing substituents at the para-position are particularly effective, due to captodative stabilization.28 Both 4-arylpyridines and 4-cyanopyridines have found numerous applications as catalysts for organic reactions of diborons.29 Scheme 1.4. Captodative stabilization vs. spin delocalization in N-borylpyridinyl radicals.a,27-28 a Captodative effects illustrated by blue (electron donating) and red (electron withdrawing) moieties. The ability of the pyridine ligand to accept an electron via a π-bond is critical: Examples of trialkylamine-stabilized boryl radicals are relatively few. Although (–)- sparteine was proposed to stabilize a boryl radical (as an explanation for an undesired racemization process), another nucleophile was present in the reaction, and the active species was not determined (Scheme 1.5).3 6 Scheme 1.5. Racemization of organoboranes induced by nucleophiles.a,30 a Both (–)-sparteine and iPr2NCO2Li were present, and it was not determined which caused racemization. N-Borylpyridinyl radicals retain much of the reducing ability of diborons. Using these radicals, a wide variety of compounds can be reductively dearomatized (pyrazines),32 aromatized (quinones),28 diborylated (diazenes),28 or deoxygenated (sulfoxides)28 (Scheme 1.6). Scheme 1.6. Reactions of N-borylpyridinyl radicals.28,31,32 7 Another recent example describes 4-cyanopyridine-catalyzed reactions with B2pin2, which are proposed to proceed via N-borylpyridinyl radical intermediates.17,28,31 Spectroscopic evidence was provided for transient populations of regiochemically and stereochemically undefined N-boryl pyridinyl radical dimers31 – their presence is consistent with the mechanistic hypothesis (Scheme 1.7). Scheme 1.7. N-Borylpyridinyl radicals and reversible dimerization via radical recombination.31 Formation of pyridinyl radical dimers has generally only been previously observed previously with metal-mediated reductions (typically alkali metals) of pyridinium cations (with rare exceptions, such as a dithionite-mediated reduction of N-methyl-4- cyanopyridinium cations).33 8 Scheme 1.8. Concerted [3,3]-sigmatropic reaction mechanism from a diboron complex.34,35,36 Sigmatropic Reactions. Concerted, diboron-mediated sigmatropic reactions (Scheme 1.8) are relatively uncommon. These reactions are attractive targets for investigation, as they proceed through closed transition states that often offer greater levels of stereocontrol than other reaction types, such as those with open transition states or radical mechanisms. Deoxygenative borylations of allylic alcohols by diborons in the presence of catalytic base are proposed to proceed through a [3,3]-sigmatropic rearrangement and are highly stereoselective.34 A reductive imine coupling using B2(4-t-Bu-cat)2, reported initially by Baker and Wescott (Scheme 1.9a), was also proposed to proceed through a [3,3]-sigmatropic rearrangement. Aldehydes were also found to be reactive, and underwent a pinacol rearrangement after the reductive coupling.35 Much later, diastereoselective B2pin2-mediated reductive dimerizations of isoquinolines and 3,4-dihydroisoquinolines were also reported (Scheme 1.10a),36 and only one diastereomer was generated, in stark contrast to the low diastereoselectivity observed with metal-mediated reactions (Scheme 1.10b)37 Also noteworthy is that cyclization onto the allyl tether was not observed, providing evidence against a radical mechanism (Scheme 1.10a). 9 Scheme 1.9. Diboron-mediated reductive couplings of imines.35,38 Scheme 1.10. Reductive couplings of isoquinolines with (a) diborons vs. (b) metals.36,37 This transformation was also highly enantioselective when chiral diboron reagents were employed. This work was expanded to the enantioselective reductive coupling of imines to afford vicinal diamines (Scheme 1.9b).38 While the scope of the substituent on 10 the imino carbon was expansive, the N-substituents were limited to N-Me and N-H. These reactions were highly selective for the thermodynamic diastereomer. However, selectivity for the kinetic product has yet to be observed. In fact, to the best of our knowledge, this challenge has not been overcome for reductive imine couplings using any known set of reductants (including transition metals, photoredox chemistry, and other methods). Scheme 1.11. Reductive coupling transition state from a B2pin2•2(isoquinoline) complex.36 This limitation is an opportunity for the development of new reductive coupling reactions, as vicinal diamines (1,2-diamino compounds) are a common part of numerous significant and stereochemically complex molecules. Vicinal diamines are found in approved drugs, drug candidates, and various ligands for synthetic procedures (Figure 1.2).39 Some promising antiviral drug candidates containing vicinal diamine motifs are unfortunately difficult to synthesize in useful quantities, and the routes to these compounds are frequently not amenable to analog synthesis. Many of these are natural products and their derivatives, notorious for the substantial challenges they typically offer to the inspired or enterprising chemist. Alas, Nature does not design molecules with synthetic feasibility in mind. 11 Figure 1.2. Significant molecules containing the vicinal diamine motif.39 Hence, new methods of synthesizing vicinal diamines to form complex ring structures, or to exploit pseudosymmetry buried deep within a retrosynthesis, are of great interest. Inspired by the pinacol coupling reaction, reductive imine coupling reactions were developed as a means to synthesize vicinal diamines. Reports of progress in this area have surfaced periodically over the last few decades, but many of these reactions are hampered by harsh conditions, limited scope and/or poor functional group tolerance, and requirements for stoichiometric quantities of metal reductants (Scheme 1.12a) or expensive reagents such as samarium (II) iodide (Scheme 1.12b).40-44 12 Scheme 1.12. A metal-mediated aza-pinacol coupling.40,41 Photoredox pinacol and aza-pinacol reactions also generate copious amounts of organic waste that can sometimes be difficult to separate from the product.45,46 Additionally, imines, aldehydes, and ketones react under identical conditions, and so to avoid undesired reactions with a ketone or aldehyde present elsewhere in the molecule, one would have to add a protection and deprotection step to the overall sequence. Inspired by the chemistry of diboron diolates (including the pyridine radical and isoquinoline and imine dimerization examples), their versatile applications in reductive chemistry,1 and the utility of vicinal diamines as a target, we sought to develop a new, operationally simple, highly chemoselective aza-pinacol reaction, employing only reagents known to degrade into non-toxic materials under aqueous workup conditions. Many diboron diolates tolerate exposure to air, and so their ease of use is alluring to synthetic chemists. 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Silylation de l'isoquinoléine: influence des conditions opératoires sur l'obtention de nouveaux hétérocycles siliciés. Canadian Journal of Chemistry, 1993, 71, 754–762. (38) Zhou, M.; Li, K.; Chen, D.; Xu, R.; Xu, G.; Tang, W. Enantioselective Reductive Coupling of Imines Templated by Chiral Diboron. J. Am. Chem. Soc. 2020, 142, 10337–10342. (39) Kotti, S. R. S. S.; Timmons, C.; Li, G. Vicinal Diamino Functionalities as Privileged Structural Elements in Biologically Active Compounds and Exploitation of their Synthetic Chemistry. Chem. Biol. Drug. Des. 2006, 67, 101–114. (40) Alexakis, A.; Aujard, I.; Mangeney, P. Practical and Efficient Synthesis of C2 Symmetrical Diamines with Zn/Me3SiCl. Synlett 1998, 8, 873–874. (41) Ebran, J.-P.; Hazell, R. G.; Skrydstrup, T. Samarium diiodide-induced intramolecular pinacol coupling of dinitrones: synthesis of cyclic cis-vicinal diamines. Chem. Commun. 2005, 5402–5404. (42) Yamamoto, Y.; Hattori, R.; Itoh, K. Highly trans-selective intramolecular pinacol coupling of dials catalyzed by bulky Cp2TiPh. Chem. Commun. 1999, 0, 825–826. 19 (43) Taniguchi, N.; Hata, T.; Uemura, M. Enantiomerically Pure Cyclic trans-1,2-Diols, Diamines, and Amino Alcohols by Intramolecular Pinacol Coupling of Planar Chiral Mono-Cr(CO)3 Complexes of Biaryls. Angew. Chem. Int. Ed. 1999, 38, 1232–1235. (44) Khan, N. H.; Zuberi, R. K.; Siddiqui, A. A. Reduction of Schiff's Bases and Phenylhydrazones by Zinc Dust. Synth. Commun. 1980, 10, 363–371. (45) Nakajima, M.; Fava, E.; Loescher, S.; Jiang, Z.; Rueping, M. Photoredox-Catalyzed Reductive Coupling of Aldehydes, Ketones, and Imines with Visible Light. Angew. Chem. Int. Ed. 2015, 54, 8828–8832. (46) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chem. Rev. 2013, 113, 5322–5363. 20 Chapter 2. Diboron-Mediated Stereodivergent Synthesis of All Diastereomers of 2,3- Diaryltetrahydroquinoxalines via Reductive Cyclization of Diimines Introduction. Vicinal diamines (1,2-diamino compounds) have versatile applications ranging from chiral ligands in catalysis1-3 to important motifs in druglike molecules.4 Many methods have been developed for their synthesis, including the reductive coupling of imines. Reductive coupling processes typically use metal-based reductants and proceed through diradical intermediates.5-10 Kinetic control over diastereoselectivity is rarely observed, and diastereomeric ratios of the obtained diamines are typically low for intermolecular reactions. In 2002, Baker, Broene, and Wescott reported the serendipitous discovery of diboron reagents as alternative reductants for intermolecular reductive imine coupling reactions, with moderate to high diastereoselectivity for the trans-diamine.11 As shown in Scheme 2.1a, reactions for imines and B2(4-tBu-cat)2 (4-tBu-cat = 4-tert-butylcatecholato) in THF afforded vicinal diamines upon aqueous workup. Electron-rich aromatic imines were found to be most reactive, while longer reaction times and lower yields were reported for electron-deficient or bulky imines, limiting its scope (and practical use). More recently (2020), Xu and Tang reported an enantioselective reductive coupling of sterically unhindered imines (HN=CHR or MeN=CHR) using chiral diborons.12 This work followed their previous report of enantioselective and diastereoselective B2pin2- mediated reductive dimerizations of isoquinolines and 3,4-dihydroisoquinolines (Scheme 2.1b).13 For both reactions, a concerted, [3,3]-sigmatropic rearrangement mechanism was 21 proposed.11,13 The high diastereoselectivity (>99:1 dr) of the isoquinoline coupling reaction contrasts the low diastereoselectivities for most metal-mediated reductive couplings of isoquinolines.14 Scheme 2.1. Imine and isoquinoline reductive couplings related to this work. 22 Highly diastereoselective intramolecular imine couplings can also be achieved with Mn/TFA, as shown in the work of Mercer and Sigman.7 The reduction of benzaldehyde- derived diimine 1 yielded 2a as the sole product (Scheme 2.1c). An intramolecular diradical combination mechanism (resulting from 1e– reduction of protonated iminium ions) is proposed to proceed through a chair-like transition state, consistent with the observed diastereoselectivity. Although effective, the outcome of this reaction is limited to one diastereomer only. In this chapter, we describe the intramolecular reductive cyclizations of diimine 1 mediated by diborons, where all three possible diastereomers (2a-2c) can be made selectively by simply varying the solvent and the structure of the diboron reagent (Scheme 2.1d). This is the first report of diastereocontrol enforced by solvent or the ligands on a boron reagent (including related reactions, such as allylborations15). Discussion of a Potential Mechanism. Scheme 2.2. Reductive [3,3]-sigmatropic rearrangement of a diimine-diboron complex. It is proposed that two mechanisms may be operative depending on the solvent. The first mechanism, favored in aprotic solvents (DMF or DCM), is a [3,3]-sigmatropic rearrangement (Scheme 2.2) that can afford two different kinetic diastereomers depending on both a) the relative rate of E/Z imine isomerization vs. reductive cyclization, and b) competing A1,3 strain between the imine and the cyclohexane ring vs. the imine and the 23 diboron. The second mechanism (Scheme 2.3a), favored in protic solvents (MeOH), is an ionic pathway that proceeds through an open transition state that affords the thermodynamic diastereomer 2a (Scheme 2.3). Scheme 2.3. Proposed mechanism for formation of 2a and heterolytic cleavage of pyridine diboron alkoxide complexes.16 The reaction of 1 with B2cat2 in MeOH gives 2,3-diaryltetrahydroquinoxaline 2a with high diastereoselectivity (>99% 2a) in 79% yield (Scheme 2.4). The [3,3]-sigmatropic rearrangement transition state requires E/Z imine isomerization (Scheme 2.5) to give the 24 relative stereochemistry for 2a. Attempts to model a transition state involving 1-(Z,E) and B2cat2 led to severe steric clashes (A1,3 strain) between the Z-imine and the cyclohexane ring. Thus, the ionic mechanism (Scheme 2.3a) is a more plausible pathway for the selective formation of 2a under the conditions in Scheme 2.4. Given the report that heterolytic B–B bond cleavage readily generates N-boryl pyridyl anions from pyridine diboron alkoxide complexes16 (Scheme 2.3b), it is proposed that monocoordinate diimine diboron alkoxide complexes may undergo a similar process, driving nucleophilic cyclization onto a tethered iminium moiety via accumulation of negative charge on the N- borylimino carbon (Scheme 2.3a). In contrast, the reaction of 1 with B2cat2 in DMF affords the cis-product 2b as the major component (24:5.3:1, 2b:2c:2a) in a diastereomeric mixture also containing 2a and 2c (99% yield). Models of a putative [3,3]-sigmatropic transition state for B2cat2 and 1- (E,E) leading to 2b do not reveal steric problems like those encountered for 2a. The observed stereoselectivity can be explained by a concerted [3,3]-sigmatropic rearrangement of a E,E-diimine-diboron complex that proceeds through the boat-like transition state shown in Scheme 2.4. The reaction of 1 with B2hmp2 in DCM affords 2c as the major component (70:8.7:1, 2c:2b:2a) in a diastereomeric mixture also containing 2a and 2b. (Selectivity with B2cat2 in DCM was lower: 17:9.3:1, 2c:2b:2a). In this case, isomerization of 1-(E,E) to 1-(E,Z) is required for the reaction to proceed through the [3,3]-sigmatropic rearrangement transition state shown in Scheme 2.4. E/Z imine isomerization has been observed at room temperature in the presence of Lewis acids such as triarylboranes17 and triarylboroxines15 (Scheme 2.5). The exact 25 mechanism for this process is unclear, though it is likely that reversible nucleophilic attack (by solvent, the imine, or traces of water or amines) on iminium ions facilitates isomerization via C–N bond rotation in the intermediate complex (aminal, hemiaminal, etc.).18 Given that the barrier to unimolecular isomerization is known to be high (~30 kcal/mol),19 it is clear that Lewis acids dramatically accelerate this process. Scheme 2.4. Reaction conditions for diastereoselective synthesis of 2a-2c along with putative transition states corresponding to the formation of each major isomer via a [3,3]- sigmatropic pathway.a a Z-imines in proposed transition states are highlighted in magenta for clarity. 26 Scheme 2.5. E/Z Isomerization of imines in the presence of boroxines.a,15 a E/Z imine stereoisomers are highlighted in magenta for clarity. This isomerization process is featured in anti-selective imine allylborations that also proceed through a [3,3]-sigmatropic rearrangement mechanism, where reaction with the Z-imine is favored due to significant A1,3 strain between substituents on the borane and the E-imine (Scheme 2.6b).15 In contrast, if the metal(loid) lacks axial substituents in the chair-like transition state,20 such as with some Cu-catalyzed allylations,21 the reaction proceeds from the E-imine and diastereoselectivity is complementary (Scheme 2.6a). However, to the best of our knowledge, diastereoselectivity for these reactions is always subject to substrate control, and solvent control has not been reported for any of these systems. We propose that a Curtin-Hammett scenario may explain the shift in diastereoselectivity with conditions for 2c vs. 2b. In a polar aprotic solvent (DMF), reductive cyclization of the E,E-diimine is faster than either E/Z imine isomerization or reductive cyclization of the E,Z-diimine, and so the reaction is selective for 2b. Stabilization of partial charges in the transition state could account for this effect. However, in a less polar solvent (DCM) and with a bulkier diboron (B2hmp2), reductive cyclization of the E,E-diimine is slower than both E/Z imine isomerization and reductive cyclization of the E,Z-diimine, and so the reaction is selective for 2c. 27 In less polar solvents, formation of polar diimine diboron complexes likely becomes more endothermic, and given that Z-imine triarylboroxine complexes are more stable than their E-imine counterparts, this may favor pathways that proceed through a Z- imine. The attenuated electrophilicity of B2hmp2 and increased A1,3 strain between the E- imine and the larger diboron diolate ligands could strengthen this effect. This dynamic kinetic resolution pathway for reductive cyclization of the diimine bears some resemblance to that proposed for anti-selective imine allylborations.15 Scheme 2.6. Role of A1,3 strain in controlling diastereoselectivity in Scheme 2.2.a,20,21 a Important A1,3 interactions are highlighted in magenta for clarity. Conclusions. We have discovered a new reductive coupling of diimines where control over relative stereochemistry can be influenced by both the solvent and structure of the diboron reagent used. This reaction was used to prepare all three possible diastereomers of 2,3- 28 diaryltetrahydroquinoxalines. It is proposed that the diboron-mediated reductive dynamic kinetic resolution of diimine 1 in aprotic solvents (DMF, DCM) proceeds via E/Z imine isomerization and [3,3]-sigmatropic rearrangement of a diimine-diboron complex, while in protic solvents (MeOH), an ionic mechanism is operative. This is the first report of solvent control over the relative stereochemistry of a reaction where the product-determining step is preceded by E/Z imine isomerization. Chapter 3 describes investigations of the scope of this chemistry, while Chapter 4 describes computational exploration of the two mechanisms discussed above, and Chapter 5 describes improved preparation of diboron reagents that could be useful in this chemistry. Experimental Section. General. All reactions were carried out under a nitrogen atmosphere unless otherwise noted. All reagents were obtained from commercial sources and were used as obtained without further purification unless otherwise specified. Additionally, dichloromethane, dimethylformamide, methanol, and anhydrous diethyl ether were obtained from commercial sources and used without further purification. Yields refer to isolated yields of compounds estimated to be ≥95% pure as determined by 1H NMR analysis unless otherwise noted. The yields reported in the manuscript and supporting information describe the result of a single experiment. Compound 1 was prepared by literature procedures.22 29 2a (±)-(2S,3S,4aR,8aR)-2,3-Diphenyldecahydroquinoxaline (2a). B2cat224 (118.9 mg, 0.5 mmol) was added to a 4 mL vial, followed by a stir bar and 0.5 mL MeOH. (±)- (1E,1E′)-N,N′-((1R,2R)-Cyclohexane-1,2-diyl)bis(1-phenylmethanimine) (1)22 (72.6 mg, 0.25 mmol) was added and the vial flushed with N2 before sealing with a PTFE cap. After stirring the reaction mixture for 3 hours, solvent was removed in vacuo. The residue was quenched with 1 mL 1 M HCl and extracted 3x with 2 mL Et2O (discarding the organic layer), and then basified with 1 mL 6 M NaOH. The aqueous layer was then extracted 3x with 2 mL Et2O. The combined organic extracts were dried with NaCl/Na2SO4, filtered, and then the solvent removed in vacuo to afford 2a (57.8 mg, 79%) as an off-white solid. Spectral data were consistent with literature values.23 2b (±)-(2R,3S,4aR,8aR)-2,3-Diphenyldecahydroquinoxaline (2b). B2cat224 (118.9 mg, 0.5 mmol) was added to a 4 mL vial, followed by a stir bar and 0.5 mL DMF. Diimine 1 (72.6 mg, 0.25 mmol) was added and the vial flushed with N2 before sealing with a PTFE cap. After stirring the reaction mixture for 1 hour, solvent was removed in vacuo. The residue was quenched with 1 mL 1 M HCl and extracted 3x with 2 mL Et2O (discarding 30 the organic layer), and then basified with 1 mL 6 M NaOH. The aqueous layer was then extracted 3x with 2 mL Et2O. The combined organic extracts were dried with NaCl/Na2SO4, filtered, and then the solvent removed in vacuo to afford 2b as the major component (24:5.3:1, 2b:2c:2a) in a diastereomeric mixture also containing 2a and 2c (73.0 mg, 99%) as a pale-yellow oil. Spectral values for [H-2b+][HB(C6F5)3] have previously been reported.25 For 2b: 1H NMR (500 MHz, CDCl3) δ 7.68–7.63 (m, 2H), 7.32–7.26 (m, 2H), 7.21–7.11 (m, 5H), 7.09–7.04 (m, 1H), 4.64 (d, J = 4.0 Hz, 1H), 4.20 (d, J = 4.0 Hz, 1H), 2.92–2.86 (m, 1H), 2.69 (ddd, J = 11.0, 9.0, 3.5 Hz, 1H), 1.88–1.17 (m, 10H); 13C{1H} NMR (126 MHz, CDCl3) δ 141.9, 141.6, 130.1, 127.9, 127.5, 127.0, 126.6, 126.6, 64.1, 63.1, 63.1, 53.5, 32.2, 32.2, 24.9, 24.9. 2c (±)-(2R,3R,4aR,8aR)-2,3-Diphenyldecahydroquinoxaline (2c). B2hmp226 (66.5 mg, 0.25 mmol) was added to a 4 mL vial, followed by a stir bar and 0.25 mL DCM. Diimine 1 (36.3 mg, 0.125 mmol) was added and the vial flushed with N2 before sealing with a PTFE cap. After stirring for 24 hours, solvent was removed in vacuo. The residue was quenched with 1 mL 1 M HCl and extracted 3x with 2 mL Et2O (discarding the organic layer), and then basified with 1 mL 6 M NaOH. The aqueous layer was then extracted 3x with 2 mL Et2O. The combined organic extracts were dried with NaCl/Na2SO4, filtered, and then the solvent removed in vacuo to afford 2c as the major component (70:8.7:1, 2c:2b:2a) in a diastereomeric mixture also containing 2a and 2b (23.8 mg, 65%) as a pale- 31 yellow oil. Diastereomeric ratios were determined via spectral deconvolution using the line fitting protocol in MNova 14.2.0 (Mestrelab Research, S.L.; Santiago de Compostela, Spain) using Gaussian/Lorentzian peak shapes and simulated annealing. Relative stereochemistry was assigned by 1D NOESY experiments. For 2c: 1H NMR (500 MHz, CDCl3) δ 7.69 (ddd, J = 8.1, 1.2, 1.2 Hz, 4H), 7.39 (dd, J = 7.7, 7.7 Hz, 4H), 7.34–7.22 (m, 2H), 4.53 (s, 2H), 2.74–2.57 (m, 2H), 1.77–1.63 (m, 4H), 1.59 (ddd, J = 12.7, 2.3, 2.3 Hz, 2H), 1.35–1.09 (m, 4H); 13C{1H} NMR (126 MHz, CDCl3) δ 144.5, 128.3, 127.7, 126.6, 58.5, 54.8, 32.3, 25.0. 32 APPENDIX 33 Spectral Data 34 35 36 37 38 39 40 41 REFERENCES 42 REFERENCES (1) Zhang, W.; Loebach, J. L.; Wilson, S. 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Organometallics 2013, 32, 1971–1978. (26) The Commonwealth of Australia Commonwealth Scientific and Industrial Research Organization US6346639, 2002, B1. 45 Chapter 3. Activation of Tetraalkoxydiborons by B2O3: Scope and Reactivity Introduction. Previously (Chapter 2) we reported diimine reductive coupling reactions using diboron diolates where relative stereochemistry could be controlled by choice of solvent and influenced by the ligands on the diboron (catecholate vs. 2-hydroxybenzyl alcoholate). Herein we discuss new methods to alter the reactivity and selectivity of tetraalkoxydiborons via a unique activation strategy employing B2O3 or B3O3(OMe)3 (trimethoxyboroxine). Modification of the reactivity of a diboron employed in synthetic organic reactions without changing the ligand or solvent has not previously been reported. Additionally, preliminary studies as to the nature of the active intermediate are discussed. Scope of the Diboron and Additives. Initial investigations of the scope of the diboron used isobutyraldehyde-derived imine 3 as the coupling substrate, with a variety of diborons (Table 3.1). Unfortunately, no reaction occurred with B2pin2 (Entry 13) or the relatively sterically unhindered diborons B2eg2 (Entry 5) and B2(OMe)4 (Entry 9). However, full conversion occurred within 48 hours with B2(OH)4 in DMF at 80 °C, affording a 1:1 mixture of the monoamine 2e– reduction product (the isobutylbenzylamine) 4b and the desired dimer 4a (Entry 1). Aromatic heterocycles, aldimines, ketones, and aldehydes are known to be reduced by diborons such as B2(OH)4 in the presence of H2O,1-3 and in this case, this pathway produces the amine 4b as an unwanted side-product. This reduction can even break aromaticity (see Scheme 3.1 for an example from the literature1), highlighting the power of wet B2(OH)4 as a reductant. However, B2(OH)4 exists in solution in equilibrium with 46 H2O and its anhydride B4O2(OH)4 (Scheme 3.2),4 so suppressing the unwanted 2e– reduction pathway by removing H2O proved challenging. Table 3.1. Screen of diborons and additives for reductive coupling of imine 3.a Entry Solvent Diboron Additive Temp Time Conv. 4a:4b d.r. (˚C) (h) (~%) 1 DMF B2(OH)4 80 48 100 1:1 - 2 DMF B2(OH)4 25 1 40 1:1 - 3 DMF B2(OH)4 B2O2 25 1 60 1:1 - 4 DMF B2(OH)4 B2O3 25 8 90 10:1 1.2:1 5 MeCN B2eg2 25 24 0 - - 6 MeCN B2eg2 B2O3 25 24 trace - - 7 MeCN B2eg2 B3O3(OMe)3 25 24 60 10:0 - 8 MeCN B2eg2 B3O3Me3 25 1 50 10:0 - 9 MeCN B2(OMe)4 25 1 0 - - 10a MeCN B2(OMe)4 B2O3 25 0.2 90 10:0 - 10b MeCN B2(OMe)4 B2O3 25 1 100 10:0 1.2:1 11a MeCN B2(OMe)4 B3O3(OMe)3 25 0.2 90 10:0 - 11b MeCN B2(OMe)4 B3O3(OMe)3 25 1 100 10:0 1.3:1 12 MeCN B2(OMe)4 B3O3Me3 25 1 100 10:0 - 13 MeCN B2pin2 60 72 0 - - a Conversion to 4a and 4b was estimated by GC-MS analysis. Diastereomeric ratios were determined by 1H NMR analysis. Scheme 3.1. Wet B2(OH)4 as an aromaticity-breaking reductant.1 47 Scheme 3.2. Equilibrium between B2(OH)4 and its anhydride.4 The ratio of 4a to 4b was unaffected by using dry DMF or adding desiccants such as Na2SO4 or MgSO4 (not shown in Table 3.1). Similarly, addition of boron monoxide5 (B2O2) had no apparent effect on selectivity (Entry 3 – self-condensation of 3 accounts for a third of conversion). However, addition of boric anhydride (B2O3) dramatically improved selectivity for 4a (Entry 4). Unfortunately, diastereoselectivity was poor (ratios estimated by 1H NMR analysis). (Notably, the reaction also became very warm – failure to carefully control large scale reactions could result in violent exotherms.) Only trace conversion to the dimer occurred with B2eg2 in MeCN (preferable to DMF for practical reasons) even with addition of B2O3 (Entry 6), but trimethoxyboroxine (B3O3(OMe)3) resulted in partial conversion (Entry 7), and trimethylboroxine (B3O3Me3) triggered a drastic increase in the reaction rate (Entry 8 – monoamine side product 4b was not detected). Similarly, no reaction occurred with B2(OMe)4 (Entry 9), but addition of B2O3, B3O3(OMe)3, or B3O3Me3 resulted in high conversion in minutes without external heating (Entries 10-12). Unfortunately, diastereoselectivity was poor, like the previous reaction with B2(OH)4/B2O3 in DMF. We elected to use B2(OMe)4 for further exploration of the scope of this chemistry, as it allowed us to avoid the tedious extraction protocols required when DMF is employed as the solvent (as B2(OH)4 is insoluble in MeCN), and to avoid the high cost of B3O3Me3 (needed for rapid conversion with B2eg2). In addition to its enhanced solubility and easier 48 workup, the boron byproducts derived from reductive coupling of imines using B2(OMe)4 are easily removed by azeotropic distillation with methanol. Little difference in conversion, chemoselectivity, and diastereoselectivity was noted between conditions employing B2O3 or B3O3(OMe)3 (Entries 10-11). Scope of the Imine Substrate. Next, the scope of the reaction with respect to imine substrate was explored (Table 3.2). Aromatic vicinal N,N’-diallyldiamines 6, 8, and 10 were afforded in good yield, but low diastereoselectivity, from imines 5, 7, and 9, respectively (Entries 1-3). In some cases B3O3(OMe)3 was used for operational simplicity (no waiting for an hour for B2O3 to dissolve). As mentioned above, its performance is nearly identical to B2O3. The reaction appears to be tolerant of different substituents on the 4-position of the phenyl ring of the imine substrate (Entries 1-3, imines 5, 7, and 9). Linear N-allylaldimine 11 (Entry 4) and α,-unsaturated aldimine 17 (Entry 8) afforded complex mixtures, while the bulky aliphatic aldimine 16 was unreactive (Entry 7). Interestingly, no ring-opened products were observed with imine 14 (Entry 6). This example provided crucial mechanistic information, as the formation of 15 is inconsistent with a radical mechanism for the reductive coupling. 49 Table 3.2. Scope of imine coupling partners. Entry (imine) R Additive Yield (%) d.r. (major:minor) 1 (5) p-MeOC6H4 B2O3 64 1.2:1 (6a:6b) 2 (7) Ph B2O3 51 1.1:1 (8a:8b) 3 (9) p-BrC6H4 B2O3 65 1:1.4 (10a:10b) 4 (11) n-Pr B2O3 Complex mixture - 5 (12) i-Pr B3O3(OMe)3 73 1.7:1a (13) 6 (14) c-Pr B3O3(OMe)3 65 1.5:1a (15) 7 (16) t-Bu B3O3(OMe)3 No reaction - 8 (17) E-styryl - Complex mixture - a The relative stereochemistry for the major diastereomer has not been resolutely assigned. This reaction can also be used to construct heterocyclic structures, such as piperazines and diazepanes. While attempts to reductively couple aromatic diimine 18 (Scheme 3.3) only afforded complex mixtures (instead of the trans-diphenylpiperazine), the reductive intramolecular coupling of aliphatic diimine 19 afforded the trans- diisopropylpiperazine 20a in good yield and 3:1 (20a:20b) diastereomeric ratio. 50 Scheme 3.3. Construction of piperazines, I. Aromatic diimine 2 (a ring fused analog of 18) (Scheme 3.4, see Chapter 2) cyclized to afford the highly strained trans-diastereomer 2c and the cis-diastereomer 2b in a 2:1 ratio. When diimine 21 was utilized, in contrast with Scheme 3.3, no trace of trans-22 (22a) was detected, the product of reported diastereoselective metal-mediated reductions6 and our prior report of the reaction of diimine 1 with B2cat2 in methanol. The cis-diastereomer 22b was obtained exclusively, a surprising result given the steric interactions between cis- 1,2 orientations of isopropyl groups in six-membered rings. Diimine 23 (Scheme 3.4) was unreactive, possibly because of steric hindrance. 51 Scheme 3.4. Construction of piperazines, II. Trans-1,4-diazepanes could also be synthesized by this method (Scheme 3.5). Diimines 24 and 26 were reductively coupled to afford diphenyl (25a) and di-isopropyl- 1,4-diazepanes (27) in good yield and diastereoselectivity, respectively. The relative stereochemistry of 25a was determined by comparison to its cis-diasteromer (25b, prepared by literature methods).6 The relative stereochemistry of 25b was established by adding a large excess of benzaldehyde to a CDCl3 solution of this diastereomer. NMR analysis of the aminal derivative and its symmetry revealed the literature product to be the cis- diastereomer 25b which was distinct from 25a (see Experimental Section for further details). 52 Scheme 3.5. Construction of 1,4-diazepanes by diboron-mediated reductive coupling of imines.a a These substrates were added slowly to a rapidly stirred solution of the diboron to avoid erosion of yield via formation of aminal side products. Inspired by the novelty of this chemistry and the scope of the reaction, we next sought to investigate the composition of the active diboron intermediate. As B2O3 is known to react with B(OMe)3 to form trimethoxyboroxine7 (Scheme 3.6), it is possible a similar transformation is occurring in situ with B2(OMe)4 during this reaction to form borylboroxine 28 (Scheme 3.7, insertion). Boroxines are known to be more electrophilic than their parent boronic acids and esters, increasing the rate of many reactions, and could theoretically accelerate this transformation.8 Scheme 3.6. Reported formation of trimethoxyboroxine.7 NMR analysis of the reaction of B2(OMe)4 with 1 equiv of B2O3 in CD3CN revealed a new set of 1H, 13C, and 11B resonances that were shifted slightly from those of B2(OMe)4, 53 as well as resonances consistent with formation of B3O3(OMe)3. However, it was unclear whether B2O3 was being incorporated into the new product (the proposed active species), forming a borylboroxine (28, Scheme 3.7, insertion) whose resonances coincided with those of B3O3(OMe)3, or if B2O3 was driving the formation of a “bis-pyrodiborate” derivative (29) of B2(OMe)4 (Scheme 3.7, metathesis). Notably, the latter structure is similar to B4O2(OH)4 (Scheme 3.8) and numerous other known compounds.9-16 Scheme 3.7. Reaction of B2(OMe)4 with B2O3: insertion vs. metathesis. Scheme 3.8. Prior reports of bis-pyrodiborate structures and analogs.9-16 As such, we sought a boron-free reagent to perform the proposed metathesis reaction and try to generate the active boron intermediate. Gratifyingly, we found that the 54 reaction of B2(OMe)4 with 1 equiv TFAA in CD3CN at room temperature (Scheme 3.9) proceeded to full conversion, forming a single product whose 1H-, 13 C-, and 11 B-NMR resonances were indistinguishable from the new resonances observed after the reaction of B2(OMe)4 with B2O3. Addition of imine 12 resulted in rapid reductive coupling, consistent with the formation of the active intermediate. Scheme 3.9. Reaction of B2(OMe)4 with TFAA. Although boroxines containing a B-B bond have never been reported, triborylboroxine 30 was considered as an alternative to the proposed bis-pyrodiborate structure 29 (Scheme 3.10a). The proportionate energy of the computational model for triborylboroxine 30 was 10.6 kcal/mol higher than that for the bis-pyrodiborate structure 29, while the triborylboroxine derivative (32) of known compound 3117 (Scheme 3.10b) was 27.4 kcal/mol higher. However, it is possible the reaction is subject to kinetic control, and so the insights afforded here are limited. Further efforts to characterize the tentatively proposed bis-pyrodiborate will be necessary for its structure to be assigned. 55 Scheme 3.10. Relative energies of bis-pyrodiborates and analogs.a a DFT quantum chemical calculations were carried out using the Gaussian 16 software package18 for solution- phase optimizations and calculation of harmonic vibrational frequencies (at 298.15 ˚K) with the M06-2X functional19-21 and the 6-31g(d,p) basis set. Frequency calculations were performed to ensure that one imaginary frequency exists for all transition states and no imaginary frequencies exist for all local minima. Solvation effects were included by performing optimizations and frequency calculations with the SMD model for acetonitrile. Conclusions. We have developed a new method for enhancing the reactivity of diborons without changing the ligands that enable reductive coupling reactions of a wide variety of imines that fail to react with diboron diolates such as B2pin2 or B2eg2. While diastereocontrol is poor for intermolecular reactions, unusual diastereochemical outcomes are often observed for intramolecular reactions, such as those that construct substituted piperazines and 1,4- diazepanes. Future work should include studies to determine the structure of the active intermediate under our conditions. 56 Experimental Section. Computational Methods. DFT quantum chemical calculations were carried out using the Gaussian 16 software suite (Revision A.03)18 using the M06-2X19-21 functional and the 6-31G(d,p) basis set for all atoms. Structures were minimized until program default convergence limits were reached. Gaussian 16 was utilized for solution-phase optimizations and calculation of harmonic vibrational frequencies (at 298.15 ˚K). The frequency calculations were performed to ensure that one imaginary frequency for all transition states and no imaginary frequencies for all local minima. Solvation effects were included by performing optimizations and frequency calculations with the SMD model for acetonitrile. General: All reactions were carried out under a nitrogen atmosphere in flame-dried glassware unless otherwise noted. All reagents, unless noted otherwise, were obtained from commercial sources and were used as obtained. THF was purified by distillation before use. Acetonitrile, dichloromethane, dimethylformamide, and anhydrous diethyl ether were obtained from commercial sources and used without further purification. Boron monoxide was prepared as previously described in the literature.5 Yields refer to isolated yields of compounds estimated to be ≥95% pure as determined by 1H NMR analysis unless otherwise noted. The yields reported in this chapter describe the result of a single experiment. General Procedure: Reductive Dimerization of Imine Substrates with B2(OMe)4 and B2O3 A 1-dram vial was charged with a stir bar and (B2O2)n (27 mg, 1 mmol). MeOH (10 µL, 0.25 mmol) was added, followed by CH(OMe)3 (120 µL, 1.1 mmol) and TFA (4 µL, 0.05 mmol). The vial was briefly flushed with nitrogen and capped, sealed 57 with Teflon tape, and stirred at 60 °C for 1-2 hours (until virtually all solid material had dissolved–the solution remained slightly cloudy). It was returned to room temperature, uncapped, and quickly B2O3 (35 mg, 0.5 mmol) was added, and then the mixture was briefly flushed with nitrogen and capped, sealed with Teflon tape and stirred at room temperature for 1 hour. (This solution can be stored on the bench for several days.) The vial was then uncapped, the mixture was quickly diluted with acetonitrile (0.25 mL), and the imine was added (0.5 mmol) with rapid stirring. The vial was then briefly flushed with nitrogen and capped. (WARNING: THESE REACTIONS BECOME VERY WARM – FAILURE TO CONTROL LARGE SCALE REACTIONS COULD RESULT IN VIOLENT EXOTHERMS.) After the reaction was complete, the mixture was diluted with MeOH (2 mL) and the solvent removed in vacuo. MeOH was then added, and the solvent removed in vacuo again. The residue was then dissolved in DCM, filtered through a small plug of basic alumina, and the solvent removed in vacuo to afford the title compound. 6a (±)-(1R,2R)-N,N′-Diallyl-1,2-bis(4-methoxyphenyl)ethane-1,2-diamine (6a). The general procedure (reaction time: 48 h) was employed for the reductive dimerization of N-allyl-1-(4-methoxyphenyl)methanimine22 (5) (88 mg, 0.5 mmol). The title compound was isolated by silica flash chromatography (56 mg, 64%) as a mixture of diastereomers (1.2:1 6a:6b d.r.), isolated as a clear colorless oil. Relative stereochemistry was assigned by comparison to spectral data reported for 8a23. Spectral data is for the mixture of 58 diastereomers (we were unable to fully and separately assign the spectral data for each diastereomer): 1H NMR (500 MHz, CDCl3) δ 7.26–7.22 (m, 4H), 6.95–6.91 (m, 4H), 6.90– 6.86 (m, 4H), 6.71–6.67 (m, 4H), 5.86 (dddd, J = 16.9, 10.2, 6.5, 5.4 Hz, 2H), 5.65 (dddd, J = 17.1, 10.3, 6.8, 5.1 Hz, 2H), 5.12–5.01 (m, 4H), 4.99–4.88 (m, 4H), 3.81 (s, 6H), 3.74 (s, 2H), 3.73 (s, 6H), 3.64 (s, 2H), 3.12 (dddd, J = 14.1, 5.4, 1.6, 1.6 Hz, 2H), 3.01–2.93 (m, 4H), 2.80 (dddd, J = 14.4, 6.8, 1.3, 1.3 Hz, 2H); 13C{1H} NMR (126 MHz, CDCl3) δ 159.0, 158.3, 137.1, 136.8, 133.1, 132.7, 129.4, 128.9, 115.6, 115.6, 113.8, 113.3, 67.5, 66.9, 55.2, 55.1, 49.9, 49.5. 8a (±)-(1R,2R)-N,N′-Diallyl-1,2-diphenylethane-1,2-diamine (8a). The general procedure (reaction time: 2 h) was employed for the reductive dimerization of N-allyl-1- phenylmethanimine24 (7) (73 mg, 0.5 mmol). The title compound was isolated by silica flash chromatography (37 mg, 51%) as a mixture of diastereomers (1.1:1 8a:8b d.r.), isolated as a clear colorless oil. Relative stereochemistry was assigned by comparison of spectral data to literature values.23 Spectral data is for each diastereomer: 8a: 1H NMR (500 MHz, CDCl3) δ 7.18–7.09 (m, 6H), 7.07–7.00 (m, 4H), 5.87 (dddd, J = 16.9, 10.2, 6.5, 5.4 Hz, 2H), 5.13–5.02 (m, 4H), 3.71 (s, 2H), 3.14 (dddd, J = 14.2, 5.4, 1.6, 1.6 Hz, 2H), 2.99 (dddd, J = 14.0, 6.6, 1.3, 1.3 Hz, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 141.1, 137.1, 127.9, 127.9, 126.9, 115.7, 68.2, 50.0. 8b: 1H NMR (500 MHz, CDCl3) δ 7.37–7.24 (m, 10H), 5.67 (dddd, J = 17.1, 10.3, 6.7, 5.1 Hz, 2H), 5.00–4.88 (m, 4H), 3.84 (s, 2H), 3.00 59 (dddd, J = 14.4, 5.1, 1.6, 1.6 Hz, 2H), 2.83 (dddd, J = 14.4, 6.7, 1.3, 1.3 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 140.7, 136.7, 128.4, 128.3, 127.6, 115.6, 67.4, 49.6. 10b (±)-(1R,2S)-N,N′-Diallyl-1,2-bis(4-bromophenyl)ethane-1,2-diamine (10b). The general procedure (reaction time: 2 h) was employed for the reductive dimerization of N-allyl-1-(4-bromophenyl)methanimine25 (9) (112 mg, 0.5 mmol). The title compound was isolated by silica flash chromatography (73 mg, 65%) as a mixture of diastereomers (1.4:1 10b:10a d.r.), isolated as a clear colorless oil. Relative stereochemistry was assigned by comparison to spectral data reported for 8a. Spectral data is for the mixture of diastereomers (we were unable to fully and separately assign the spectral data for each diastereomer): 1H NMR (500 MHz, CDCl3) δ 7.45–7.41 (m, 4H), 7.31–7.25 (m, 4H), 7.12– 7.07 (m, 4H), 6.91–6.85 (m, 4H), 5.83 (dddd, J = 16.9, 10.2, 6.6, 5.4 Hz, 2H), 5.68 (dddd, J = 17.1, 10.3, 6.7, 5.1 Hz, 2H), 5.11–5.03 (m, 4H), 5.03–4.92 (m, 4H), 3.79 (s, 2H), 3.61 (s, 2H), 3.10 (dddd, J = 14.1, 5.4, 1.6, 1.6 Hz, 2H), 3.01 (dddd, J = 14.4, 5.2, 1.6, 1.6 Hz, 2H), 2.94 (dddd, J = 14.1, 6.6, 1.4, 1.4 Hz, 2H), 2.84 (dddd, J = 14.4, 6.8, 1.3, 1.3 Hz, 2H); 13 C{1H} NMR (126 MHz, CDCl3) δ 140.0, 139.4, 136.7, 136.4, 131.4, 131.2, 130.1, 129.6, 121.4, 120.8, 116.0, 67.5, 66.5, 49.9, 49.5. 60 13 N,N′-Diallyl-2,5-dimethylhexane-3,4-diamine (13). A 1-dram vial was charged with a stir bar, B2(OMe)4 (76 µL, 0.5 mmol), B3O3(OMe)3 (73 µL, 0.5 mmol), and MeCN (0.5 mL). N-Allyl-2-methylpropan-1-imine26 (12) (55.6 mg, 0.5 mmol) was added dropwise over 5 minutes with rapid stirring, and the vessel was then briefly flushed with nitrogen and capped. After stirring for 2 hours, solvent was removed in vacuo, and 5 mL Et2O added (resulting in precipitation) and solvent removed in vacuo again. The solid residue was washed with Et2O (3 x 2 mL). 0.4 mL MeOH was added followed by 4.0 mL Et2O, and the solution then filtered through a basic alumina plug, flushing three times with Et2O. Solvent was then removed in vacuo, the residue redissolved in Et2O and filtered through a cotton plug, and solvent removed in vacuo again to afford the title compound (41 mg, 73%) as a mixture of diastereomers (1.7:1 d.r.), isolated as a clear colorless oil. Spectral data is for the mixture of diastereomers (we were unable to fully and separately assign the spectral data for each diastereomer): 1H NMR (500 MHz, CDCl3) δ 5.94–5.84 (m, 4H), 5.19–5.00 (m, 8H), 3.32 (dddd, J = 13.8, 6.0, 1.4, 1.4 Hz, 2H), 3.25 (dddd, J = 7.1, 5.8, 1.5, 1.5 Hz, 4H), 3.20 (dddd, J = 13.7, 6.1, 1.5, 1.5 Hz, 2H), 2.30 (dd, J = 3.2, 1.3 Hz, 2H), 2.26–2.22 (m, 2H), 1.95–1.86 (m, 2H), 1.83–1.74 (m, 2H), 0.94 (d, J = 3.6 Hz, 6H), 0.93 (d, J = 3.7 Hz, 6H), 0.92 (d, J = 6.9 Hz, 6H), 0.90 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 137.7, 137.7, 115.3, 115.2, 63.8, 62.8, 53.2, 52.8, 31.2, 29.3, 21.7, 19.4, 18.9, 18.5. 61 15 N,N′-Diallyl-1,2-dicyclopropylethane-1,2-diamine (15). A 1-dram vial was charged with a stir bar, B2(OMe)4 (76 µL, 0.5 mmol), B3O3(OMe)3 (73 µL, 0.5 mmol), and MeCN (0.5 mL). (E)-1-cyclopropyl-N-methylmethanimine27 (14) (54.6 mg, 0.5 mmol) was added dropwise over 5 minutes with rapid stirring, and the vessel was then briefly flushed with nitrogen and capped. After stirring for 2 hours, solvent was removed in vacuo, and 5 mL Et2O added (resulting in precipitation) and solvent removed in vacuo again. The solid residue was washed with Et2O (3 x 2 mL). 0.4 mL MeOH was added followed by 4.0 mL Et2O, and the solution then filtered through a basic alumina plug, flushing three times with Et2O. Solvent was then removed in vacuo, the residue redissolved in Et2O and filtered through a cotton plug, and solvent removed in vacuo again to afford the title compound (36 mg, 65%) as a mixture of diastereomers (1.6:1 d.r.), isolated as a clear colorless oil. Spectral data is for the mixture of diastereomers (we were unable to fully and separately assign the spectral data for each diastereomer): 1H NMR (500 MHz, CDCl3) δ 5.94–5.81 (m, 4H), 5.19–5.01 (m, 8H), 3.46 (dddd, J = 14.1, 5.7, 1.6, 1.6 Hz, 2H), 3.34 (dddd, J = 14.2, 5.9, 1.5, 1.5 Hz, 2H), 3.27 (dddd, J = 14.1, 6.2, 1.5, 1.5 Hz, 2H), 3.17 (dddd, J = 14.1, 6.1, 1.5, 1.5 Hz, 2H), 1.88–1.84 (m, 2H), 1.84–1.80 (m, 2H), 1.03–0.93 (m, 2H), 0.82–0.73 (m, 2H), 0.61–0.51 (m, 4H), 0.51–0.40 (m, 4H), 0.31–0.21 (m, 4H), 0.21–0.08 (m, 4H); 13 C{1H} NMR (126 MHz, CDCl3) δ 137.8, 137.5, 115.5, 115.1, 66.0, 64.7, 50.6, 50.4, 14.2, 12.6, 4.6, 4.3, 2.6, 2.5. 62 20a (±)-(2R,3R)-2,3-Diisopropylpiperazine (20a). The general procedure (reaction time: 1 h) was employed for the reductive dimerization of (1E,1E′)-N,N′-(ethane-1,2- diyl)bis(2-methylpropan-1-imine)28 (19) (42.1 mg, 0.25 mmol). This procedure afforded the title compound (32 mg, 75%) as the major diastereomer (3:1 20a:20b d.r.), isolated as a clear yellow oil. Spectral data is for the mixture of diastereomers (we were unable to fully and separately assign the spectral data for each diastereomer): 1H NMR (500 MHz, CDCl3) δ 2.97 (d, J = 8.1 Hz, 2H), 3.01–2.93 (m, 2H), 2.70 (d, J = 8.1 Hz, 2H), 2.75–2.67 (m, 2H), 2.55–2.48 (m, 2H), 2.34 (dd, J = 1.3, 1.3 Hz, 2H), 1.99–1.89 (m, 4H), 1.01 (d, J = 6.7 Hz, 6H), 0.96–0.92 (m, 6H), 0.95 (dd, J = 6.8, 1.3 Hz, 6H), 0.84 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 63.0, 62.9, 47.5, 45.2, 28.0, 27.0, 21.4, 20.9, 20.6, 15.2. 2c 2b (±)-(2R,3R,4aR,8aR)-2,3-Diphenyldecahydroquinoxaline (2c), and (±)- (2R,3S,4aR,8aR)-2,3-Diphenyldecahydroquinoxaline (2b). The general procedure (reaction time: 72 h) was employed, with a modified workup, for the reductive dimerization of (±)-(1E,1E′)-N,N′-((1R,2R)-cyclohexane-1,2-diyl)bis(1-phenylmethanimine)29 1 (72.6 mg, 0.25 mmol). The reaction was quenched with 0.5 M aq. HCl (2 mL). A large amount of white precipitate formed, which was removed via filtration, and basified with 1 M aq. NaOH (4 mL). NaCl was added until the solution became saturated, then extracted with 63 Et2O (3 x 3 mL), the organic layers combined and dried with Na2SO4, and solvent removed in vacuo to afford 2c (36 mg, 50%) as a single diastereomer, isolated as an white crystalline solid: 1H NMR (500 MHz, CDCl3) δ 7.69 (ddd, J = 8.1, 1.2, 1.2 Hz, 4H), 7.39 (dd, J = 7.7, 7.7 Hz, 4H), 7.34–7.22 (m, 2H), 4.53 (s, 2H), 2.74–2.57 (m, 2H), 1.77–1.63 (m, 4H), 1.59 (ddd, J = 12.7, 2.3, 2.3 Hz, 2H), 1.35–1.09 (m, 4H); 13C{1H} NMR (126 MHz, CDCl3) δ 144.4, 128.3, 127.7, 126.7, 58.5, 54.9, 32.3, 25.0. The filtrate was then basified with 1 M aq. NaOH (4 mL) and NaCl added until the solution became saturated. It was then extracted with Et2O (3 x 3 mL), the organic layers combined and dried with Na2SO4, and solvent removed in vacuo to afford 2b as the major component of a mixture with 2c (28 mg, 38%, 3:1 dr), isolated as a pale yellow oil. For 2b: 1H NMR (500 MHz, CDCl3) δ 7.65–7.59 (m, 2H), 7.26 (dd, J = 5.8, 2.5 Hz, 2H), 7.19–7.10 (m, 5H), 7.08–7.01 (m, 1H), 4.61 (d, J = 4.0 Hz, 1H), 4.18 (d, J = 4.1 Hz, 1H), 2.86 (ddd, J = 10.6, 9.1, 3.8 Hz, 1H), 2.70–2.63 (m, 1H), 1.83–1.17 (m, 10H); 13C{1H} NMR (126 MHz, CDCl3) δ 141.9, 141.5, 130.1, 127.8, 127.5, 126.9, 126.6, 126.6, 64.1, 63.1, 63.0, 53.5, 32.2, 32.1, 24.9, 24.9. The combined yield of diastereomers 2c and 2b was 64 mg (88% yield) with a 2:1 (2c:2b) overall dr. 22b (±)-(2R,3S,4aR,8aR)-2,3-Diisopropyldecahydroquinoxaline (22b). The general procedure (reaction time: 18 h) was employed for the reductive dimerization of (1E,1E′)- N,N′-((1R,2R)-cyclohexane-1,2-diyl)bis(2-methylpropan-1-imine)30 21 (55.6 mg, 0.25 mmol). This procedure afforded the title compound (42 mg, 75%) as the sole diastereomer, isolated as an off-white oil: 1H NMR (500 MHz, CDCl3) 2.64 (ddd, J = 6.8, 3.2, 1.1 Hz, 64 1H), 2.61 (dd, J = 9.9, 2.0 Hz, 1H), 2.45–2.39 (m, 1H), 2.27–2.17 (m, 2H), 1.82–1.60 (m, 4H), 1.59–1.51 (m, 1H), 1.35–1.17 (m, 4H), 1.0 (dd, J = 17.6, 6.8 Hz, 6H), 0.9 (dd, J = 19.7, 6.5 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 68.6, 63.3, 58.7, 55.6, 32.3, 32.0, 29.1, 26.5, 25.0, 24.9, 22.7, 21.2, 20.6, 20.3. 25a (±)-(2R,3R)-2,3-Diphenyl-1,4-diazepane (25a). A 1 dram vial was charged with a stir bar, B2(OMe)4 (76 µL, 0.5 mmol), B3O3(OMe)3 (73 µL, 0.5 mmol), and MeCN (0.5 mL). The imine (1E,1E′)-N,N′-(propane-1,3-diyl)bis(1-phenylmethanimine)31 24 (62.6 mg, 0.25 mmol) was added gradually, with rapid stirring, over a period of 30 minutes, and the vessel flushed with N2 and capped after each addition. Stirring was then continued for another 30 minutes (total reaction time = 1 hour), and the reaction quenched with 1 M aq. HCl (1 mL). The solution was extracted with Et2O (3 x 2 mL), and the organic layers discarded, and then basified with 6 M aq. NaOH (1 mL). After gas evolution subsided, the solution was extracted with Et2O (3 x 2 mL), and the organic layer dried with NaCl and Na2SO4. Solvent was removed in vacuo to afford the title compound (54 mg, 86%) as a mixture of diastereomers (3.5:1), isolated as a yellow oil. Spectral data is for the major diastereomer: 1H NMR (500 MHz, CDCl3) δ 7.4–6.9 (m, 10H), 3.7 (s, 2H), 3.3 (ddd, J = 13.5, 4.8, 4.8 Hz, 2H), 3.2 (ddd, J = 13.5, 8.2, 8.2 Hz, 2H), 2.0–1.7 (m, 4H); 13C{1H} NMR (126 MHz, CDCl3) δ 143.0, 127.9, 127.7, 127.0, 75.2, 47.4, 31.7. 65 APPENDICES 66 APPENDIX A: Spectral Data 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 APPENDIX B: GC-MS Results for Table 3.1. Entry 1 Entry 2 99 Entry 3 Entry 4 100 Entry 5 Entry 6 101 Entry 7 Entry 8 102 Entry 9 Entry 10a 103 Entry 11a Entry 12 104 Entry 13 105 APPENDIX C: Computational Coordinates. The below coordinates use the M06-2X functional and the 6-31g(d,p) basis set with the SMD model for acetonitrile. B2(OMe)4 B2OMe4_freqdp M062X/6-31G(d,p) E(RM062X) = -510.2014527 Zero-point correction= 0.182586 (Hartree/Particle) Thermal correction to Energy= 0.196153 Thermal correction to Enthalpy= 0.197097 Thermal correction to Gibbs Free Energy= 0.142453 Sum of electronic and ZPE= -510.018866 Sum of electronic and thermal Energies= -510.005300 Sum of electronic and thermal Enthalpies= -510.004355 Sum of electronic and thermal Free Energies= -510.058999 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 123.088 43.757 115.008 B,0.012485,0.862721,-0.0572 B,-0.012485,-0.862721,-0.0572 O,1.088779,1.636814,0.273028 O,-1.119295,1.517117,-0.462081 O,-1.088779,-1.636814,0.273028 O,1.119295,-1.517117,-0.462081 C,2.310365,1.058009,0.706255 H,2.141907,0.218879,1.387176 H,2.879172,1.830449,1.228801 H,2.894296,0.703265,-0.147806 C,-1.119295,2.937412,-0.537493 H,-2.106394,3.251607,-0.882406 H,-0.36218,3.296668,-1.241051 H,-0.921718,3.385146,0.441144 C,1.119295,-2.937412,-0.537493 H,0.921718,-3.385146,0.441144 H,2.106394,-3.251607,-0.882406 H,0.36218,-3.296668,-1.241051 C,-2.310365,-1.058009,0.706255 H,-2.141907,-0.218879,1.387176 H,-2.879172,-1.830449,1.228801 H,-2.894296,-0.703265,-0.147806 106 B4O2(OMe)4 (29) b4o2ome4 M062X/6-31G(d,p) E(RM062X) = -710.4984307 Zero-point correction= 0.201419 (Hartree/Particle) Thermal correction to Energy= 0.218381 Thermal correction to Enthalpy= 0.219325 Thermal correction to Gibbs Free Energy= 0.156463 Sum of electronic and ZPE= -710.297011 Sum of electronic and thermal Energies= -710.280050 Sum of electronic and thermal Enthalpies= -710.279106 Sum of electronic and thermal Free Energies= -710.341967 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 137.036 55.908 132.303 B,0.86110955,1.2007384435,0.0172099256 O,1.5697484816,2.3553578005,0.0614605474 O,1.5535613226,0.0000000001,0. B,-0.8611095502,1.2007384434,-0.0172099255 O,-1.5697484818,2.3553578003,-0.0614605474 O,-1.5535613226,-0.0000000001,0. B,0.8611095502,-1.2007384434,-0.0172099255 B,-0.86110955,-1.2007384435,0.0172099256 O,1.5697484818,-2.3553578003,-0.0614605474 O,-1.5697484816,-2.3553578005,0.0614605474 C,2.9941840483,-2.3085441246,-0.0899548634 H,3.3893951925,-1.8221388754,0.8063816708 H,3.3565571453,-3.3370001355,-0.1299312872 C,-2.9941840481,-2.3085441249,0.0899548635 H,-3.356557145,-3.3370001359,0.1299312872 H,-3.3893951924,-1.8221388757,-0.8063816708 C,-2.9941840483,2.3085441246,-0.0899548634 H,-3.3565571453,3.3370001355,-0.1299312872 H,-3.3893951925,1.8221388754,0.8063816708 C,2.9941840481,2.3085441249,0.0899548635 H,3.356557145,3.3370001359,0.1299312872 H,3.3893951924,1.8221388757,-0.8063816708 H,-3.3523021594,1.7662119991,-0.9695899009 H,3.3523021592,1.7662119994,0.969589901 H,3.3523021594,-1.7662119991,-0.9695899009 H,-3.3523021592,-1.7662119994,0.969589901 107 B(OMe)3 bome3 M062X/6-31G(d,p) E(RM062X) = -370.2379722 Zero-point correction= 0.134218 (Hartree/Particle) Thermal correction to Energy= 0.143868 Thermal correction to Enthalpy= 0.144813 Thermal correction to Gibbs Free Energy= 0.098272 Sum of electronic and ZPE= -370.103754 Sum of electronic and thermal Energies= -370.094104 Sum of electronic and thermal Enthalpies= -370.093160 Sum of electronic and thermal Free Energies= -370.139701 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 90.279 29.808 97.954 B,-0.0009657041,-0.0003167871,0.0001938615 O,1.2391729113,0.572432602,0.000041736 C,1.3398715183,1.9885153086,-0.0002822636 H,0.8684316288,2.4197358164,-0.8887740455 H,2.4008474798,2.2459180336,-0.0006674269 H,0.8690090899,2.4200952196,0.8883461419 O,-0.1241246458,-1.360799626,0.0009651853 O,-1.1172691659,0.78701062,-0.0003185521 C,-2.3933530533,0.164817481,-0.0001906231 H,-2.5267351929,-0.4672310653,-0.8834878093 H,-3.1474222573,0.9542390152,-0.0106285392 H,-2.5342470462,-0.4505633566,0.8937251505 C,1.0538141484,-2.1534339024,0.0003368955 H,0.7486181959,-3.2015680982,0.0060246816 H,1.6655412656,-1.9554361053,0.8858425091 H,1.6590528275,-1.9633221555,-0.8913729018 B3O3(B(OMe)2)3 (30) brxbome23_from-b2ome4_not-symmetrized M062X/6-31G(d,p) E(RM062X) = -1065.7363152 Zero-point correction= 0.302458 (Hartree/Particle) Thermal correction to Energy= 0.328879 Thermal correction to Enthalpy= 0.329824 Thermal correction to Gibbs Free Energy= 0.240173 Sum of electronic and ZPE= -1065.433857 Sum of electronic and thermal Energies= -1065.407436 108 Sum of electronic and thermal Enthalpies= -1065.406492 Sum of electronic and thermal Free Energies= -1065.496143 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 206.375 86.577 188.687 B,-1.1925331674,0.7206754312,0.1917696817 O,0.0279660393,1.3668910492,0.2160849699 O,-1.1998607869,-0.6630019468,0.2092700215 B,1.2226840763,0.669870897,0.2549655204 B,-0.0300342837,-1.3965869024,0.2515308714 O,1.171614242,-0.7104894544,0.2771272679 B,-0.0225492606,-3.1180984867,0.243965336 O,-1.082170523,-3.9262541042,0.5377662084 O,1.1530236106,-3.7208615241,-0.0995759765 C,-2.3405976967,-3.3838114327,0.9149122218 C,1.2221482604,-5.140669395,-0.1461433115 H,-2.2441918812,-2.7114669436,1.7724701199 H,-2.9896421321,-4.2172979008,1.1912664822 H,-2.7979281237,-2.8334270757,0.0882474943 H,1.0078669227,-5.5787197155,0.8333936105 H,2.2353946813,-5.4139431505,-0.4469890326 H,0.5101046493,-5.5478918284,-0.8703073573 B,-2.6877711023,1.5711516757,0.118677289 O,-2.8670787159,2.9036066466,0.3523279768 O,-3.7895086137,0.8363035039,-0.2125251526 C,-1.7790772037,3.7423376654,0.716903072 C,-5.0550270126,1.4786672804,-0.3045766183 H,-1.2694380495,3.3685096041,1.6096819562 H,-2.1841948139,4.7337017847,0.9302379528 H,-1.0503843388,3.8212083603,-0.0944320264 H,-5.3382872205,1.932014409,0.6501520123 H,-5.7929937933,0.7209586202,-0.5749299362 H,-5.0466040892,2.2609445264,-1.0696572189 B,2.705372039,1.5463424369,0.2597500463 O,3.9557701378,1.0165539163,0.3926221075 O,2.6093851164,2.8998865662,0.1099376879 C,4.1552200216,-0.3801228704,0.5640633908 C,3.7945965326,3.6857667317,0.0963306338 H,3.6469555978,-0.7468813963,1.4603117541 H,5.2287302308,-0.5487517912,0.6716134105 H,3.7905878943,-0.9428963564,-0.299557324 H,4.3578723923,3.5682308661,1.0269734309 H,3.4987640886,4.7307861823,-0.0145476302 H,4.4443624553,3.4061135716,-0.7385661621 109 B4O2(NMe2)4 (31) b4o2nme24_antitwist M062X/6-31G(d,p) E(RM062X) = -788.1807893 Zero-point correction= 0.364858 (Hartree/Particle) Thermal correction to Energy= 0.387071 Thermal correction to Enthalpy= 0.388015 Thermal correction to Gibbs Free Energy= 0.315114 Sum of electronic and ZPE= -787.815932 Sum of electronic and thermal Energies= -787.793719 Sum of electronic and thermal Enthalpies= -787.792775 Sum of electronic and thermal Free Energies= -787.865676 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 242.890 80.292 153.433 B,1.2219001866,-0.7860360962,-0.3499017548 B,-1.1481552504,-0.8557338118,0.1311510297 B,-1.1551825698,0.8535939895,-0.1206784142 B,1.2200768077,0.7997041366,0.3361122765 N,-2.1859619197,-1.6387516045,0.6819724865 C,-3.4046798385,-1.0868842806,1.2399786375 C,-2.0911139415,-3.0786211039,0.8441294533 H,-4.2939670092,-1.4276800393,0.6921056187 H,-3.3730622094,0.0037093352,1.2162226275 H,-3.5200169201,-1.4030046868,2.2851829647 H,-2.9351949325,-3.5799295001,0.3528401099 H,-2.1147311982,-3.3571891569,1.9060992931 H,-1.1618530643,-3.4426671569,0.4062336129 N,-2.2039238585,1.6296172008,-0.6605972175 C,-2.1204172891,3.070079334,-0.8237170936 C,-3.4246674554,1.0695696857,-1.2058757592 H,-1.1891216124,3.4403737412,-0.3954907155 H,-2.9626927591,3.565746758,-0.3236828011 H,-2.1569269763,3.348426945,-1.8853806211 H,-3.3855025116,-0.0207864879,-1.1824660803 H,-3.5530083788,1.3848488109,-2.2498181556 H,-4.3104610318,1.4044318905,-0.6487613577 N,2.2633674987,-1.3941397332,-1.0841093864 C,2.1760958768,-2.7433861919,-1.613671538 C,3.4791502333,-0.7103992591,-1.4785747525 H,1.2482310257,-3.2127037884,-1.2871560514 H,3.0221923839,-3.3508913602,-1.2669461561 110 H,2.2022846765,-2.7373413222,-2.7114853948 H,3.4416103016,0.3367689453,-1.1736420184 H,3.5962706116,-0.7448624297,-2.5697987017 H,4.3702294604,-1.1766362436,-1.0361529127 N,2.2648098262,1.4147603186,1.0598096131 C,2.1739814616,2.763486958,1.5901036789 C,3.4891374183,0.7392140067,1.4417779794 H,2.2120691661,2.7578179626,2.6875661627 H,1.2394284091,3.2263287576,1.2735697762 H,3.0120733362,3.3767481525,1.2341861064 H,3.6172380333,0.7746263344,2.5317329333 H,4.3724916619,1.2113122274,0.9901724323 H,3.455454057,-0.3082263787,1.1373169909 O,0.0306177165,1.5219819387,0.1990788113 O,0.0386845675,-1.5161781773,-0.2010575721 B3O3(B(NMe2)2)3 (32) b3o3bnme23_rst_nosymm M062X/6-31G(d,p) E(RM062X) = -1182.2327813 Zero-point correction= 0.546184 (Hartree/Particle) Thermal correction to Energy= 0.581076 Thermal correction to Enthalpy= 0.582020 Thermal correction to Gibbs Free Energy= 0.475343 Sum of electronic and ZPE= -1181.686597 Sum of electronic and thermal Energies= -1181.651706 Sum of electronic and thermal Enthalpies= -1181.650761 Sum of electronic and thermal Free Energies= -1181.757439 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 364.630 123.211 224.521 B,-1.3970147611,-0.1109065542,0.0001437801 B,0.8018129708,-1.1519428476,-0.0008355068 B,0.6038353261,1.2728034796,-0.0017419248 B,-3.1152978937,-0.2515894198,0.007889003 N,-3.8743963948,0.6109145559,0.8596524903 N,-3.7328213649,-1.2266612539,-0.8362045708 C,-3.2840048483,1.3241449077,1.9761310702 C,-5.271220825,0.9635231657,0.6781798944 C,-5.056149729,-1.7930165759,-0.6448582675 C,-3.0435254517,-1.8439372086,-1.9531887949 H,-3.806184775,1.0853704148,2.9132911245 H,-3.3472524684,2.4127835037,1.8353803367 111 H,-2.2348115035,1.0536238838,2.1021636736 H,-5.3828796911,2.0546209631,0.7398476445 H,-5.9254347733,0.526577291,1.4463696966 H,-5.6273900715,0.6488593947,-0.3032907424 H,-5.4500811978,-1.5362900219,0.3390045945 H,-4.9961938354,-2.8881529423,-0.7056514779 H,-5.7758199641,-1.4644109848,-1.4084359419 H,-2.0480153401,-1.4173239373,-2.0820612531 H,-3.5982040586,-1.6904637198,-2.889510755 H,-2.9398245042,-2.9290331349,-1.8092835931 B,1.7775738212,-2.5734822111,-0.0078646029 N,1.3981590711,-3.6732724102,0.8241233285 N,2.9350173289,-2.615667164,-0.8464094076 C,0.4811301159,-3.5309691014,1.9387678518 C,1.7832976853,-5.0586460177,0.6221801887 C,4.0794524371,-3.4904108264,-0.6630279991 C,3.134548056,-1.6998214343,-1.9533186031 H,0.9432761401,-3.8797547757,2.8729782288 H,-0.4318645897,-4.1240177161,1.7849351002 H,0.1946504048,-2.4878388357,2.0782736299 H,0.8898150349,-5.6958327529,0.6708141022 H,2.4838705691,-5.4233267255,1.3872148531 H,2.2363114126,-5.1971380822,-0.3600252845 H,4.047936406,-3.9716606273,0.3149993213 H,5.0027973757,-2.8976430617,-0.7143120454 H,4.150283735,-4.2691753633,-1.4360045078 H,2.2740690259,-1.0408766048,-2.0754425566 H,3.2741667132,-2.2481376343,-2.8955920494 H,4.0287435412,-1.0782013341,-1.8020643831 B,1.3425447118,2.830855776,-0.0016071796 N,0.8115763363,3.8484774053,-0.8545487579 N,2.4666810984,3.0610810257,0.8521927486 C,-0.0606568915,3.5540325595,-1.9753962638 C,0.9855444412,5.278725873,-0.6734109765 C,3.4719727431,4.0923726264,0.6672211849 C,2.7846023697,2.1996704917,1.9748961073 H,0.3589766805,3.9457570416,-2.9126367357 H,-1.0505653366,4.0139841033,-1.8437289433 H,-0.1946120343,2.478120727,-2.0944686375 H,0.0089307582,5.7765601756,-0.7444103282 H,1.6358954516,5.7299874194,-1.4365503928 H,1.3991603459,5.4983620197,0.3113821863 H,3.3821309776,4.5505593286,-0.3182123099 H,4.4720904849,3.6433053958,0.7370293825 H,3.4177432152,4.8833870292,1.4290603864 H,2.0262686319,1.4255811178,2.0999153066 112 H,2.8328628821,2.7758659208,2.9095697039 H,3.7605530412,1.7111426732,1.841647511 O,-0.5833477423,-1.2345797918,0.0005265749 O,-0.7762473402,1.1300867447,-0.0054097063 O,1.3681480458,0.1145660571,0.0023424936 113 REFERENCES 114 REFERENCES (1) Xia, Y.-T.; Sun, X.-T.; Zhang, L.; Luo, K.; Wu, L. 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Untersuchungen über Schiffsche Basen, II: Darstellung von 1.2- Diamino-cyclopropanen und von Schiffschen Basen dieser Diamine. Chem. Ber. 1965, 98, 2691–2700. (30) Pirali, T.; Callipari, G.; Ercolano, E.; Genazzani, A. A.; Giovenzana, G. B.; Tron, G. C. A Concise Entry into Nonsymmetrical Alkyl Polyamines. Org. Lett. 2008, 10, 4199–4202. 117 Chapter 4. Probing the Origins of Diastereoselectivity Using Computational Models and New Experimental Conditions Introduction. Intrigued by the mechanistic questions raised by our previous report (Chapter 2) of diboron-mediated reductive couplings of diimine 1 where variation of solvent (and the ligands on the diboron) enables diastereoselective access to all three diastereomers of a diamine 2a-2c, we next investigated the proposed mechanisms for this reaction via computational modeling to investigate what influence choice of solvent may have on the mechanism. Scheme 4.1. Concerted [3,3]-sigmatropic rearrangement mechanism1-3 (a) and proposed transition states (b) as discussed in Chapter 2. 118 Two mechanisms were proposed in our initial report (Chapter 2): (1) A concerted [3,3]-sigmatropic rearrangement of a dicoordinate diimine-diboron complex (Scheme 4.1a), affording two potential kinetic products (2b and 2c) via a closed boat-like transition state (Scheme 4.1b), and (2) heterolytic B-B cleavage of a monocoordinate diimine- diboron complex, affording the thermodynamic product (2a) via an ionic, open chair-like transition state (Scheme 4.2b) as previously reported in the literature for pyridines4 (Scheme 4.2b). 119 Scheme 4.2. (a) Proposed ionic mechanism and transition state and (b) literature precedent.4 Investigation of the Sigmatropic Mechanism. We began by considering the concerted [3,3]-sigmatropic rearrangement mechanism. E/Z imine isomerization (which is facile in the presence of electrophilic boron reagents5) is required to access the trans-diaxial diamine (2c), but we were unable to locate a transition state for this isomerization process. Two scenarios are possible for conditions leading to the cis-diamine (2b): (1) E/Z isomerization is slower than the reductive coupling 120 step, or (2) reductive coupling of the E,E-diimine is faster than reductive coupling of the Z,E-diimine. Given prior reports of isomerization of 1,1-B2cat2 (BC[1,1]) to 1,2-B2cat2 (BC[1,2]) occurring in the presence of DBN or 4-picoline,6 it is plausible that this transformation (Scheme 4.3, below) could also proceed at a rate competitive with the reductive coupling step. This would likely proceed through a highly polar ligand reorganization step requiring the presence of a nucleophile to stabilize the buildup of positive charge during dissociation of one of the catecholate ligands. As the steric profiles of these regioisomeric forms are different, we decided to consider reductive coupling transition states derived from both. Unfortunately, we also have yet to locate a transition state for the conversion of 1,1-B2cat2 into 1,2-B2cat2. Scheme 4.3. Isomerization of 1,1-B2cat2 into 1,2-B2cat2.6 121 Figure 4.1. Dipole moments of representative examples of substrates, intermediate complexes, transition states, and products.a 1,1-B2cat2DMF (1,1-B2cat2 in DMF) Dipole moment = 0 E,E-(1)DMF (E,E-diimine 1 in DMF) Dipole moment = 1.03 122 Figure 4.1 (cont’d) IA-E,E[1,1]DMF (Intermediate monocoordinate 1,1-B2cat2-E,E-diimine 1 complex in DMF Dipole moment = 7.11 IB-E,E[1,1]DMF (Intermediate dicoordinate 1,1-B2cat2-E,E-diimine 1 complex in DMF) Dipole moment = 14.14 123 Figure 4.1 (cont’d) TS-E,E[1,1]DMF (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,E- diimine 1 complex in DMF) Dipole moment = 10.57 124 Figure 4.1 (cont’d) P-E,E[1,1]DMF (N,N-diborylated product 2c from reductive coupling transition state TS-E,E[1,1]DMF in DMF) Dipole moment = 0.96 a Dipole moments and direction are indicated by blue arrows. The strong influence solvent polarity has over reactivity and diastereoselectivity in this system offers insight into the relative energies of key intermediates and transition states, if their dipole moments are considered. Following the reaction pathway, they are: (1) Relatively non-polar: the substrate diimine and B2cat2; (2) very polar: the intermediate diimine-diboron Lewis acid-base complex, due to charge separation; (3) moderately polar: the transition state for reductive coupling, which should be less polar than the intermediate diimine-diboron Lewis acid-base complex, due to a partial shift of electron density from 125 the breaking B-B bond to the forming C-C bond. Our computational models were consistent with these predictions: intermediate dicoordinate diimine-diboron complexes IB had the highest dipole moments, and diimine 1 and B2cat2 substrates had the lowest dipole moments (Figure 4.1 and Table 4.2). Given these considerations, if formation of diimine-diboron complexes IA or IB is exothermic, non-polar solvents should accelerate the reaction. Table 4.1. Calculated energies (ΔG).a Solvent Product Diimine (1) IA1,1 IA1,2 IB1,1 IB1,2 TS1,1 TS1,2 P1,1 P1,2 Geometry MeOH 2b E,E -0.4 0.3 3.9 -4.1 18.1 16.6 -50.8 -28.7 DMF 2b E,E 2.4 2.0 8.3 0.5 21.4 18.1 -49.6 -26.6 C6H6 2b E,E 4.7 3.1 14.2 6.0 24.3 19.8 -50.9 -26.6 MeOH 2c Z,E -1.6 -0.5 2.9 -3.7 18.0 17.1 -58.2 -36.1 DMF 2c Z,E -0.5 1.5 6.9 0.4 20.5 18.8 -57.5 -34.8 C6H6 2c Z,E 2.2 3.4 13.2 5.1 21.6 19.5 -59.4 -35.8 MeOH 2a E,Z 6.7 6.8 5.6 -0.5 27.7 21.7 -51.6 -32.1 DMF 2a E,Z 10.3 9.5 10.3 3.4 29.6 23.5 -50.0 -30.6 C6H6 2a E,Z 9.3 11.5 14.4 8.6 30.7 25.6 -50.7 -31.4 MeOH 2b Z,Z 5.5 7.6 5.3 -1.2 27.4 25.0 -50.8 -29.9 DMF 2b Z,Z 8.0 9.7 9.5 2.0 30.1 26.5 -49.6 -29.0 C6H6 2b Z,Z 8.2 12.2 11.4 6.7 30.6 27.2 -50.9 -29.8 a ΔG given in kcal/mol. 1,1-B2cat2 and E,E-diimine 1 were used as the ground state. Table 4.2. Dipole moments.a Solvent Product Diimine (1) IA1,1 IA1,2 IB1,1 IB1,2 TS1,1 TS1,2 P1,1 P1,2 Geometry MeOH 2b E,E 7.13 8.58 14.38 15.11 10.41 7.05 0.94 0.82 DMF 2b E,E 7.11 8.41 14.14 14.65 10.57 7.07 0.96 0.90 C6H6 2b E,E 5.83 6.85 10.91 11.39 7.87 5.42 0.71 0.93 MeOH 2c Z,E 8.51 9.91 15.76 16.72 9.64 7.67 0.61 3.45 DMF 2c Z,E 8.55 9.48 15.67 16.22 10.47 7.88 0.70 3.22 C6H6 2c Z,E 7.53 8.26 12.55 13.17 8.46 6.63 0.69 2.56 MeOH 2a E,Z 6.65 8.11 16.04 16.30 11.17 9.70 0.66 3.14 DMF 2a E,Z 6.64 7.97 15.49 15.86 11.59 9.67 0.82 2.93 C6H6 2a E,Z 5.22 6.62 12.47 13.11 9.22 8.05 0.67 2.36 MeOH 2b Z,Z 7.99 9.61 17.69 18.43 9.68 8.02 0.94 3.34 DMF 2b Z,Z 8.05 9.38 17.26 17.93 10.08 8.10 0.96 3.08 C6H6 2b Z,Z 7.06 8.16 15.12 15.29 8.73 7.02 0.71 2.48 a ΔG given in kcal/mol. 1,1-B2cat2 and E,E-diimine 1 were used as the ground state. 126 However, experimental results indicate the reverse: polar solvents accelerate the reaction, implying that formation of diimine-diboron complexes is endothermic (or approximately thermoneutral). Consistent with these observations, our models indicated that all stereoisomers of dicoordinate diimine-1,1-B2cat2 (IB1,1) and dicoordinate diimine- 1,2-B2cat2 (IB1,2) complexes were endothermic in both DMF and benzene (Table 4.1). Figure 4.2 Concerted [3,3]-sigmatropic rearrangement transition states.a a Each of these four possible E/Z diimine configurations in diimine-diboron reductive coupling transition states have two combinations with diboron isomers (1,1- and 1,2-), signified as TS-E/Z,E/Z[1,1]/[1,2]. Consistent with observed diastereoselectivity (as illustrated by Figure 4.2 and Table 4.3) we found that the relative energies of transition states TS-E,Z leading to trans- diequatorial product (2a) were dramatically higher than those leading to either trans- diaxial product (2c) via TS-Z,E, or cis-product (2b) via TS-E,E, suggesting that this mechanism is unlikely to explain the formation of 2a. We also found that TS-Z,Z were even higher than those leading to the trans-diequatorial product (2a). Given these results, we decided to limit our discussion of transition states to TS-E,E and TS-Z,E. 127 These results reveal the likely mechanistic scenarios for each set of conditions: With polar aprotic solvents (using DMF to model conditions selective for cis- product 2b), either: (1) E/Z isomerization is slower than reductive coupling, as TS- E,E[1,1] is higher energy than TS-Z,E[1,1], or (2) diboron isomerization is faster than reductive coupling, as TS-E,E[1,2] is lower energy than TS-Z,E[1,2], TS-E,E[1,1], and TS-Z,E[1,1]. Table 4.3. Calculated transition state energies (ΔG‡).a Product Transition 1,1-B2cat2 1,2-B2cat2 1,1-B2cat2 1,2-B2cat2 1,1-B2cat2 1,2-B2cat2 State (MeOH) (MeOH) (DMF) (DMF) (Benzene) (Benzene) 2b TS-E,E 19.6 18.0 21.4 18.2 24.3 19.8 2c TS-Z,E 19.4 18.6 20.5 18.8 21.6 19.5 2a TS-E,Z 29.1 23.2 29.6 23.5 30.7 25.6 2b TS-Z,Z 28.8 26.5 30.1 26.5 30.6 27.2 a ΔG‡ given in kcal/mol. 1,1-B2cat2 and E,E-diimine 1 were used as the ground state, unless the monocoordinate intermediates IA or dicoordinate intermediates IB were lower in energy. The lowest energy transition state for each solvent is highlighted in bold. With non-polar aprotic solvents (using benzene to model conditions selective for trans-diaxial product 2a), E/Z isomerization is faster than reductive coupling, and the relative rate of diboron isomerization is unclear, as TS-Z,E[1,1] and TS-Z,E[1,2] are both lower energy than TS-E,E[1,1] or TS-E,E[1,2]. However, since the energy gap between TS-Z,E[1,2] and TS-E,E[1,2] is less than the gap between TS-Z,E[1,1] and TS-E,E[1,1], future work should consider means to reduce the rate of diboron isomerization. Future work should also include locating transition states for reductive coupling with B2hmp2 (Figure 4.3), which eliminates the aforementioned 1,2-diboron isomers from consideration. It is also expected that A1,3 strain derived from steric clashes between the diimine and this bulkier diboron will further lower the energy of TS-Z,E relative to TS-E,E, consistent with the experimentally observed improvement in selectivity for 2c with B2hmp2. 128 Figure 4.3. Structure of B2hmp2. Investigation of the Ionic Mechanism. Here we describe our preliminary investigations into the viability of the second proposed mechanism: Heterolytic B-B cleavage of a monocoordinate diimine-diboron complex, affording the thermodynamic product via an open chair-like transition state (Scheme 4.2a). The formation of the trans-diequatorial product (2a), consistent with our expectations, appears to be ruled out by our computational studies on the [3,3]-sigmatropic pathway that proceeds through concerted transition states. We found that transition states leading to 2a were significantly higher in energy in MeOH, DMF, and benzene (Table 4.3), suggesting another mechanism is operative. We postulated that catechol is present in solution (liberated by exchange with methanol) and a base is present (possibly 2a-c themselves, generated by deborylation of the N,N-diboryl diamine product by methanol or catechol), and that both components may be necessary for the reaction to proceed, as deprotonation of catechol would provide access to anionic B2cat2 complexes such as the one shown in Scheme 4.2a. 129 Scheme 4.4. Reductive coupling of 1 with added base and catechol.a a Conversion and diastereomeric ratio estimated by GC-MS analysis. To test this hypothesis, the reductive coupling was again performed with two conditions changed: a) solvent was replaced with polar aprotic DMF, and b) both catechol and Et3N were added prior to diimine 1 (Scheme 4.4). Intruigingly, unlike the system in DMF without catechol and Et3N, which affords the cis-product (2b), this system was highly selective for the trans-diequatorial product 2a (45:1.8:1, 2a:2b:2c d.r.). Catechol was essential for the dramatic reversal in diastereoselectivity (without Et3N, 9.6:3.4:1 2a:2b:2c d.r.), suggesting a change in the mechanism. Addition of Et3N alone did not reverse selectivity (1:4.9:2.9 2a:2b:2c d.r.). It is currently unclear whether Et3N plays the role of a catalyst or an initiator (due to generation of the basic diamine product throughout the reaction). We developed a substantially simplified computational system (Scheme 4.5) to establish the theoretical framework (bond distances, angles, etc.) for finding transition states for the proposed ionic mechanism for the transformation shown in Scheme 4.4. We found that formation of diimine-B2F4 complex (A) from diimine 18 and B2F4 was exothermic (–16.2 kcal/mol), as was the reaction of 18 with HF to form ionized diimine- B2F5H complex (B) (–8.2 kcal/mol). Reductive cyclization of 18 to 29b via open transition state (C) was found with a reasonable barrier (23.3 kcal/mol), while elimination of HF to 130 return to the initial diimine-B2F4 complex (A) and reductive cyclization to 29a via concerted [3,3]-sigmatropic rearrangement transition state (D) had an overall barrier of 25.6 kcal/mol (higher by 2.3 kcal/mol), suggesting that in this system, the other pathway is preferred. However, given the influence solvent and the structure of the diboron has over product selectivity (Chapter 2), it is critical to note that this system is only a demonstration of the theoretical feasibility of the ionic mechanism (not evidence that it is operative), and is intended primarily to establish a framework for models of the experimental system. Due to the difficulty of locating global minima in this experimental system (a consequence of the greatly increased conformational flexibility and atom count with the diimine, B2cat2, and added catechol), studies on the experimental system have thus far been unsuccessful. 131 Scheme 4.5. Modeling the ionic mechanism. Conclusions. We have used computational modeling to rationalize the divergent diastereochemical outcomes of diboron-mediated reductive coupling reactions of diimines (see Figure 4.4 for reaction coordinates for reactions in DMF and benzene for products 2b and 2c). It is unlikely that trans-diequatorial compound 2a is formed via a concerted [3,3]- sigmatropic rearrangement of a diimine-diboron complex due to significant A1,3 strain in these transition states. It is proposed that an alternative, ionic mechanism accounts for its selective synthesis in protic solvents. 132 Figure 4.4. Generalized reaction coordinates for reactions in DMF and benzene for products 2b and 2c (relative energies given in kcal/mol). 133 Figure 4.4 (cont’d) 134 Figure 4.4 (cont’d) 135 Figure 4.4 (cont’d) 136 Experimental Section. Computational Methods. DFT quantum chemical calculations for diimine 1, complexes, and transition states, were carried out using the Gaussian 16 software suite (Revision A.03)7 using the M06-2X functional8-10 and the 6-31G(d,p) basis set for all atoms. Structures were minimized until program default convergence limits were reached. Gaussian 16 was also utilized for solution-phase optimizations and calculation of harmonic vibrational frequencies (at 298.15 ˚K). The frequency calculations were performed to ensure that one imaginary frequency exists for all transition states and no imaginary frequencies exist for all local minima. Solvation effects were included by performing optimizations and frequency calculations with the SMD model for DMF and benzene. Diimine 3 (Scheme 4.5) complexes, and transition states used the 6-31+G(d,p) basis set with the SMD model for acetonitrile. Coordinates are provided in Appendix C for this chapter. Reductive coupling of 1 with added base and catechol. B2cat211 (59.5 mg, 0.25 mmol) and catechol (27.5 mg, 0.25 mmol) were added to a 4 mL vial, followed by a stir bar and 0.25 mL DMF. Then, while stirring, Et3N (3.5 µL, 0.025 mmol) was added, followed by diimine 1 (36.3 mg, 0.125 mmol), and the vial flushed with N2 before sealing with a PTFE cap. After stirring the reaction mixture for 45 minutes, a sample was withdrawn (5-10 µL) and diluted with 1.0 mL MeOH. GC-MS analysis of this solution found 90% conversion of 1, and that the reaction was highly selective for 2a (45:1.8:1 2a:2b:2c d.r.). Reductive coupling of 1 with added catechol. B2cat211 (59.5 mg, 0.25 mmol) and catechol (27.5 mg, 0.25 mmol) were added to a 4 mL vial, followed by a stir bar and 0.25 137 mL DMF. Then, while stirring, diimine 1 (36.3 mg, 0.125 mmol) was added, and the vial flushed with N2 before sealing with a PTFE cap. After stirring the reaction mixture for 1.25 hours, a sample was withdrawn (5-10 µL) and diluted with 1.0 mL MeOH. GC-MS analysis of this solution found 98% conversion of 1, and that the reaction was highly selective for 2b (9.6:3.4:1 2b:2c:2a d.r.). Reductive coupling of 1 with added base. B2cat211 (59.5 mg, 0.25 mmol) was added to a 4 mL vial, followed by a stir bar and 0.25 mL DMF. Then, while stirring, Et3N (35 µL, 0.25 mmol) was added, followed by diimine 1 (36.3 mg, 0.125 mmol), and the vial flushed with N2 before sealing with a PTFE cap. After stirring the reaction mixture for 1 hour, a sample was withdrawn (5-10 µL) and diluted with 1.0 mL MeOH. GC-MS analysis of this solution found 93% conversion of 1, and that the reaction was selective for 2c (1:4.9:2.9 2b:2c:2a d.r.). 138 APPENDICES 139 APPENDIX A: Bond Distances Table 4.4. Bond distance change from intermediate complex to transition state (Å).a Solvent Product Transition State B-B1,1 B-B1,2 C-C1,1 C-C1,2 DM1,1 DM1,2 MeOH 2b TS-E,E 0.27 0.35 -1.82 -1.85 -3.97 -8.06 DMF 2b TS-E,E 0.27 0.35 -1.78 -1.77 -3.57 -7.58 C6H6 2b TS-E,E 0.28 0.33 -1.67 -1.73 -3.03 -5.97 MeOH 2c TS-Z,E 0.31 0.34 -1.53 -1.66 -6.12 -9.05 DMF 2c TS-Z,E 0.29 0.33 -1.43 -1.58 -5.20 -8.34 C6H6 2c TS-Z,E 0.24 0.33 -1.32 -1.70 -4.09 -6.54 MeOH 2a TS-E,Z 0.26 0.26 -1.50 -1.96 -4.88 -6.60 DMF 2a TS-E,Z 0.24 0.26 -1.29 -1.90 -3.90 -6.19 C6H6 2a TS-E,Z 0.26 0.24 -1.37 -1.80 -3.24 -5.06 MeOH 2b TS-Z,Z 0.33 0.34 -1.42 -1.38 -8.00 -10.42 DMF 2b TS-Z,Z 0.32 0.34 -1.31 -1.33 -7.18 -9.83 C6H6 2b TS-Z,Z 0.27 0.32 -0.78 -1.21 -6.39 -8.27 a DM = dipole moment. Table 4.5. B-B bond distances (Å). Solvent Product Diimine (1) IA1,1 IA1,2 IB1,1 IB1,2 TS1,1 TS1,2 P1,1 P1,2 Geometry MeOH 2b E,E 1.72 1.69 1.73 1.73 2.00 2.09 5.57 2.67 DMF 2b E,E 1.72 1.69 1.73 1.75 2.00 2.09 5.56 2.67 C6H6 2b E,E 1.72 1.69 1.73 1.75 2.01 2.08 5.57 2.67 MeOH 2c Z,E 1.71 1.69 1.73 1.74 2.04 2.07 5.49 2.69 DMF 2c Z,E 1.71 1.69 1.74 1.73 2.02 2.07 5.78 2.69 C6H6 2c Z,E 1.71 1.69 1.74 1.72 1.98 2.05 5.48 2.69 MeOH 2a E,Z 1.72 1.69 1.73 1.73 1.99 1.99 4.70 2.70 DMF 2a E,Z 1.72 1.69 1.74 1.73 1.98 1.99 4.98 2.69 C6H6 2a E,Z 1.72 1.69 1.73 1.73 1.99 1.98 5.07 2.69 MeOH 2b Z,Z 1.71 1.69 1.74 1.72 2.07 2.06 5.57 2.70 DMF 2b Z,Z 1.71 1.69 1.74 1.72 2.06 2.06 5.56 2.70 C6H6 2b Z,Z 1.71 1.69 1.74 1.73 2.01 2.05 5.57 2.70 Table 4.6. C-C bond distances (Å). Solvent Product Diimine (1) IA1,1 IA1,2 IB1,1 IB1,2 TS1,1 TS1,2 P1,1 P1,2 Geometry MeOH 2b E,E 3.82 4.00 4.67 4.51 2.85 2.66 1.55 1.61 DMF 2b E,E 3.82 4.02 4.60 4.49 2.82 2.71 1.55 1.61 C6H6 2b E,E 3.80 3.52 4.51 4.55 2.84 2.82 1.55 1.61 MeOH 2c Z,E 4.47 4.04 4.59 4.43 3.06 2.77 1.54 1.59 DMF 2c Z,E 4.59 3.77 4.57 4.41 3.13 2.83 1.54 1.59 C6H6 2c Z,E 4.50 3.76 4.51 4.61 3.18 2.91 1.54 1.59 MeOH 2a E,Z 3.96 4.08 4.31 4.47 2.82 2.51 1.54 1.59 DMF 2a E,Z 3.97 4.08 4.16 4.45 2.87 2.55 1.56 1.59 C6H6 2a E,Z 3.94 4.00 4.18 4.46 2.81 2.67 1.56 1.59 MeOH 2b Z,Z 4.59 4.17 4.49 4.15 3.08 2.76 1.55 1.61 DMF 2b Z,Z 4.59 4.12 4.46 4.15 3.16 2.82 1.55 1.61 C6H6 2b Z,Z 4.63 4.08 4.02 4.11 3.24 2.90 1.55 1.61 140 APPENDIX B: Computational Coordinates The below coordinates use the M06-2X functional and the 6-31g(d,p) basis set with the SMD model for methanol, dimethylformamide, benzene. BC[1,1]MeOH (1,1-B2cat2 in MeOH) b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -812.5933855 Zero-point correction= 0.189451 (Hartree/Particle) Thermal correction to Energy= 0.202147 Thermal correction to Enthalpy= 0.203091 Thermal correction to Gibbs Free Energy= 0.149421 Sum of electronic and ZPE= -812.403934 Sum of electronic and thermal Energies= -812.391238 Sum of electronic and thermal Enthalpies= -812.390294 Sum of electronic and thermal Free Energies= -812.443964 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 126.849 50.954 112.958 H,0.000165166,2.5158521927,-4.0888466982 C,0.0000950817,1.4317116791,-4.1022801999 C,-0.0000950817,-1.4317116791,-4.1022801999 C,0.0000463472,0.6953608417,-2.9338545125 C,0.0000464736,0.698766121,-5.2938892975 C,-0.0000464736,-0.698766121,-5.2938892975 C,-0.0000463472,-0.6953608417,-2.9338545125 H,0.0000812112,1.2305814511,-6.2395542787 H,-0.0000812112,-1.2305814511,-6.2395542787 H,-0.000165166,-2.5158521927,-4.0888466982 O,-0.0000722737,-1.1421241566,-1.630757619 O,0.0000722737,1.1421241566,-1.630757619 B,0.,0.,-0.8436190705 H,-0.000165166,2.5158521927,4.0888466982 C,-0.0000950817,1.4317116791,4.1022801999 C,0.0000950817,-1.4317116791,4.1022801999 C,-0.0000463472,0.6953608417,2.9338545125 C,-0.0000464736,0.698766121,5.2938892975 C,0.0000464736,-0.698766121,5.2938892975 C,0.0000463472,-0.6953608417,2.9338545125 H,-0.0000812112,1.2305814511,6.2395542787 H,0.0000812112,-1.2305814511,6.2395542787 H,0.000165166,-2.5158521927,4.0888466982 141 O,0.0000722737,-1.1421241566,1.630757619 O,-0.0000722737,1.1421241566,1.630757619 B,0.,0.,0.8436190705 BC[1,2]MeOH (1,2-B2cat2 in MeOH) b2cat2_1-2_meoh M062X/6-31G(d,p) E(RM062X) = -812.5909938 Zero-point correction= 0.189355 (Hartree/Particle) Thermal correction to Energy= 0.201835 Thermal correction to Enthalpy= 0.202779 Thermal correction to Gibbs Free Energy= 0.150369 Sum of electronic and ZPE= -812.401639 Sum of electronic and thermal Energies= -812.389159 Sum of electronic and thermal Enthalpies= -812.388215 Sum of electronic and thermal Free Energies= -812.440625 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 126.653 51.665 110.307 O,-1.1930663301,1.4900300643,-0.0001878816 O,-1.1930696977,-1.4900202385,-0.0000029388 B,0.0000036021,0.8249662003,0.0000279868 B,-0.0000031129,-0.8249589352,-0.0000629173 O,1.1930693217,1.4900314893,-0.0001327603 O,1.193064597,-1.4900271811,0.0000554991 C,2.3352635366,-0.7060468186,0.0000681794 C,2.3352681609,0.706044287,-0.0000787296 C,3.5483286462,-1.3862634851,0.0001520855 C,3.5483337003,1.3862585251,-0.000130826 C,4.7552663177,-0.6962171074,0.000087386 H,3.5162168953,-2.4712121012,0.0002437633 C,4.7552692488,0.6962085133,-0.0000333981 H,3.5162236672,2.4712072112,-0.000230358 H,5.688872516,-1.248467988,0.0001456487 H,5.6888775707,1.2484556769,-0.0000680086 C,-2.3352696994,-0.7060388248,0.0000793902 C,-3.548333531,-1.386253392,0.0002050664 C,-2.3352660137,0.7060545922,-0.0000614761 C,-4.7552708547,-0.6962024544,0.00018842 H,-3.5162264111,-2.4712020329,0.0002882404 C,-3.5483299657,1.3862698673,-0.0000695099 C,-4.7552685331,0.6962211889,0.0000664943 H,-5.6888781675,-1.2484514027,0.0002778098 142 H,-3.5162221089,2.4712185247,-0.0001687361 H,-5.6888743547,1.2484728214,0.0000655707 BC[1,1]DMF (1,1-B2cat2 in DMF) cfc_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -812.596877 Zero-point correction= 0.189874 (Hartree/Particle) Thermal correction to Energy= 0.202530 Thermal correction to Enthalpy= 0.203474 Thermal correction to Gibbs Free Energy= 0.150023 Sum of electronic and ZPE= -812.407003 Sum of electronic and thermal Energies= -812.394347 Sum of electronic and thermal Enthalpies= -812.393403 Sum of electronic and thermal Free Energies= -812.446854 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 127.089 50.808 112.497 H,-0.0618359336,2.5148634153,4.0875615353 C,-0.0352427789,1.4310720269,4.0995684179 C,0.0352427789,-1.4310720269,4.0995684179 C,-0.0170904348,0.69573955,2.929757997 C,-0.017375414,0.6986750944,5.2910107976 C,0.017375414,-0.6986750944,5.2910107976 C,0.0170904348,-0.69573955,2.929757997 H,-0.0305396861,1.2302413972,6.2366315423 H,0.0305396861,-1.2302413972,6.2366315423 H,0.0618359336,-2.5148634153,4.0875615353 O,0.0279257629,-1.141423706,1.6311987801 O,-0.0279257629,1.141423706,1.6311987801 B,0.,0.,0.8442614863 H,0.0618359336,2.5148634153,-4.0875615353 C,0.0352427789,1.4310720269,-4.0995684179 C,-0.0352427789,-1.4310720269,-4.0995684179 C,0.0170904348,0.69573955,-2.929757997 C,0.017375414,0.6986750944,-5.2910107976 C,-0.017375414,-0.6986750944,-5.2910107976 C,-0.0170904348,-0.69573955,-2.929757997 H,0.0305396861,1.2302413972,-6.2366315423 H,-0.0305396861,-1.2302413972,-6.2366315423 H,-0.0618359336,-2.5148634153,-4.0875615353 O,-0.0279257629,-1.141423706,-1.6311987801 143 O,0.0279257629,1.141423706,-1.6311987801 B,0.,0.,-0.8442614863 BC[1,2]DMF (1,2-B2cat2 in DMF) b2cat2_1-2_dmf M062X/6-31G(d,p) E(RM062X) = -812.5932204 Zero-point correction= 0.189554 (Hartree/Particle) Thermal correction to Energy= 0.202065 Thermal correction to Enthalpy= 0.203010 Thermal correction to Gibbs Free Energy= 0.150443 Sum of electronic and ZPE= -812.403666 Sum of electronic and thermal Energies= -812.391155 Sum of electronic and thermal Enthalpies= -812.390211 Sum of electronic and thermal Free Energies= -812.442777 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 126.798 51.609 110.636 O,-1.1933532468,-1.4885184996,0.0003087531 O,-1.1933536778,1.4886129388,0.0000989657 B,0.0000197107,-0.8255900125,-0.0002383572 B,-0.0000020607,0.8256636318,-0.0000331686 O,1.193344285,-1.4885744219,-0.0000794324 O,1.1933653491,1.4886192642,-0.0001876347 C,2.3324763166,0.7065314113,-0.000241635 C,2.3324800371,-0.706491262,-0.0000994098 C,3.5468811956,1.385861238,-0.0002709578 C,3.5468586095,-1.3858596664,-0.000031594 C,4.7537534375,0.6962492212,-0.0001704272 H,3.5165211112,2.4706364698,-0.0003268166 C,4.7537473623,-0.6962679343,-0.0000897307 H,3.5164697445,-2.4706318884,0.000047283 H,5.6872508681,1.2485170449,-0.0001779318 H,5.6872381159,-1.2485461683,-0.0000408498 C,-2.3325034861,0.7065614792,-0.0001521461 C,-3.5468798823,1.385908741,-0.0003408229 C,-2.332484721,-0.7064765057,0.0000212019 C,-4.7537650256,0.6962954731,-0.0003681191 H,-3.5165168325,2.4706825947,-0.0004344742 C,-3.5468701135,-1.3858181037,0.0000036256 C,-4.7537566559,-0.6962131324,-0.0001946158 H,-5.6872556366,1.2485750971,-0.0005145222 H,-3.5165120176,-2.470593919,0.0001648347 144 H,-5.6872387867,-1.2485070911,-0.0002210181 BC[1,1]benzene (1,1-B2cat2 in benzene) cfc_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -812.5955254 Zero-point correction= 0.190125 (Hartree/Particle) Thermal correction to Energy= 0.202766 Thermal correction to Enthalpy= 0.203710 Thermal correction to Gibbs Free Energy= 0.150377 Sum of electronic and ZPE= -812.405401 Sum of electronic and thermal Energies= -812.392760 Sum of electronic and thermal Enthalpies= -812.391816 Sum of electronic and thermal Free Energies= -812.445148 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 127.237 50.746 112.248 H,-0.1101493422,2.5117991696,4.084255457 C,-0.0627929433,1.4291518907,4.098448836 C,0.0627929433,-1.4291518907,4.098448836 C,-0.0305386962,0.6952521939,2.9284714958 C,-0.0307363149,0.6979058823,5.2892385344 C,0.0307363149,-0.6979058823,5.2892385344 C,0.0305386962,-0.6952521939,2.9284714958 H,-0.0540751362,1.2285799709,6.2349611256 H,0.0540751362,-1.2285799709,6.2349611256 H,0.1101493422,-2.5117991696,4.084255457 O,0.0500088093,-1.1400737832,1.630976836 O,-0.0500088093,1.1400737832,1.630976836 B,0.,0.,0.8444972095 H,0.1101493422,2.5117991696,-4.084255457 C,0.0627929433,1.4291518907,-4.098448836 C,-0.0627929433,-1.4291518907,-4.098448836 C,0.0305386962,0.6952521939,-2.9284714958 C,0.0307363149,0.6979058823,-5.2892385344 C,-0.0307363149,-0.6979058823,-5.2892385344 C,-0.0305386962,-0.6952521939,-2.9284714958 H,0.0540751362,1.2285799709,-6.2349611256 H,-0.0540751362,-1.2285799709,-6.2349611256 H,-0.1101493422,-2.5117991696,-4.084255457 O,-0.0500088093,-1.1400737832,-1.630976836 O,0.0500088093,1.1400737832,-1.630976836 B,0.,0.,-0.8444972095 145 BC[1,2]benzene (1,2-B2cat2 in benzene) b2cat2_1-2_benzene M062X/6-31G(d,p) E(RM062X) = -812.5923852 Zero-point correction= 0.189856 (Hartree/Particle) Thermal correction to Energy= 0.202332 Thermal correction to Enthalpy= 0.203276 Thermal correction to Gibbs Free Energy= 0.150838 Sum of electronic and ZPE= -812.402529 Sum of electronic and thermal Energies= -812.390053 Sum of electronic and thermal Enthalpies= -812.389109 Sum of electronic and thermal Free Energies= -812.441547 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 126.965 51.541 110.366 O,-1.1937588339,-1.4873268215,0.0002946201 O,-1.1937524673,1.4874063009,0.0000875264 B,0.000021909,-0.8267927043,-0.0002131784 B,-0.0000054656,0.8268568985,-0.0000430018 O,1.1937443564,-1.4873882361,-0.0000620655 O,1.1937634658,1.487424734,-0.0001816513 C,2.3327027581,0.7062545936,-0.0002430059 C,2.3327107525,-0.7062167587,-0.0000850779 C,3.5466555106,1.3853166535,-0.0002794274 C,3.5466398408,-1.3853114682,-0.0000127243 C,4.7527577883,0.6959493856,-0.0001716008 H,3.5125832537,2.4695585801,-0.0003428068 C,4.7527549829,-0.695960681,-0.0000899727 H,3.5125402969,-2.4695509508,0.0000791254 H,5.6863743313,1.2476668277,-0.0001913554 H,5.6863677521,-1.2476836841,-0.0000342655 C,-2.3327322046,0.7062812267,-0.0001931245 C,-3.5466485968,1.3853647838,-0.0003397091 C,-2.3327162333,-0.7062083194,-0.000040496 C,-4.7527652844,0.6959943959,-0.0003587594 H,-3.5125779577,2.4696057117,-0.0004010677 C,-3.5466488642,-1.3852765054,-0.0000245271 C,-4.7527618141,-0.6959044204,-0.0001890348 H,-5.6863747406,1.2477233266,-0.0004737354 H,-3.5125914731,-2.4695190424,0.0001311336 H,-5.6863690632,-1.2476378264,-0.000190818 146 E,E-(1)MeOH (E,E-diimine 1 in MeOH) cydiimph2_EE_meoh M062X/6-31G(d,p) E(RM062X) = -884.5343065 Zero-point correction= 0.378938 (Hartree/Particle) Thermal correction to Energy= 0.397837 Thermal correction to Enthalpy= 0.398782 Thermal correction to Gibbs Free Energy= 0.328304 Sum of electronic and ZPE= -884.155368 Sum of electronic and thermal Energies= -884.136469 Sum of electronic and thermal Enthalpies= -884.135525 Sum of electronic and thermal Free Energies= -884.206002 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 249.647 74.440 148.332 C,4.9125242396,0.6961166937,-0.3156333221 C,3.6514440834,1.4642558439,0.0760221424 C,2.3776438973,0.7095419593,-0.3105335298 C,2.3776442589,-0.7095401833,0.3105326245 C,3.6514446254,-1.4642535841,-0.0760234089 C,4.9125245989,-0.6961139555,0.3156316863 H,3.6376133901,1.6246732016,1.1621118504 H,3.6327975245,2.4529215074,-0.3952085259 H,4.9566515658,0.5979822368,-1.4085829334 H,5.8007264264,1.2582039944,-0.0092869951 H,2.3370590996,-0.5852178898,1.40573541 H,3.6327985754,-2.4529192568,0.3952072656 H,3.6376136755,-1.6246709593,-1.162113112 H,4.9566522084,-0.5979794803,1.4085812844 H,5.8007269126,-1.2582009138,0.0092850989 H,2.3370584769,0.5852196494,-1.4057363031 N,1.2168873687,1.4296995052,0.1853285839 N,1.2168878661,-1.4296981536,-0.1853291724 C,0.2039098763,1.5034877846,-0.5792280618 H,0.2126184963,1.0885049744,-1.597777685 C,0.2039106527,-1.5034868933,0.5792277991 H,0.2126195598,-1.0885044686,1.5977775765 C,-1.0658788504,2.1314626845,-0.1629474282 C,-2.1355051289,2.1526332749,-1.0622692795 C,-1.2258666944,2.6898803273,1.1116053493 C,-3.350739981,2.7278866791,-0.6982881626 H,-2.0102958963,1.7137712678,-2.0490599387 C,-2.437693635,3.2644934,1.4732217914 147 H,-0.3928656681,2.6662918587,1.8072295268 C,-3.50244995,3.2849249641,0.5692154925 H,-4.1770197103,2.740565355,-1.4022301567 H,-2.5575835505,3.6973593976,2.4616848865 H,-4.4484009816,3.7344507768,0.8555686659 C,-1.065877707,-2.1314629595,0.1629478055 C,-2.1355035318,-2.1526344704,1.0622701725 C,-1.2258656698,-2.6898807751,-1.1116048807 C,-3.3507380662,-2.7278889144,0.6982896393 H,-2.0102942072,-1.7137723384,2.0490607644 C,-2.43769229,-3.2644948938,-1.4732207369 H,-0.3928650036,-2.6662915936,-1.8072294624 C,-3.5024481589,-3.2849273586,-0.569213932 H,-4.1770174511,-2.7405682882,1.4022320251 H,-2.5575823081,-3.6973610122,-2.4616837673 H,-4.4483989385,-3.7344539937,-0.8555666464 E,Z-(1)MeOH (E,Z-diimine 1 in MeOH) cydiimph2_EZ_meoh M062X/6-31G(d,p) E(RM062X) = -884.5265055 Zero-point correction= 0.379505 (Hartree/Particle) Thermal correction to Energy= 0.398134 Thermal correction to Enthalpy= 0.399078 Thermal correction to Gibbs Free Energy= 0.330344 Sum of electronic and ZPE= -884.147001 Sum of electronic and thermal Energies= -884.128372 Sum of electronic and thermal Enthalpies= -884.127428 Sum of electronic and thermal Free Energies= -884.196161 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 249.833 74.165 144.662 C,2.0936070703,-0.5274269693,0.4162908905 C,4.262980688,-1.5109731306,-0.4487648556 C,2.0631562244,-2.4526136747,-1.2204819219 C,3.5229432289,-2.7701145839,-0.89988508 C,1.3494489628,-1.8046133476,-0.0324401481 C,3.554145545,-0.8642835481,0.740543292 H,4.3045225846,-0.7966942095,-1.2818592428 H,2.0106423262,-1.7608567898,-2.0716879914 H,3.5653163961,-3.5207789838,-0.0994283599 H,1.3543457886,-2.4980785715,0.8258936522 H,3.5680223932,-1.5475759167,1.5997823715 148 H,2.074553038,0.1931706193,-0.4127870733 H,5.2975124392,-1.7483509349,-0.1800808817 H,1.5196330981,-3.3590662357,-1.5081697623 H,4.0099648109,-3.209958748,-1.7762474548 H,4.0667455528,0.0531609197,1.0493660817 N,-0.0081778308,-1.4539146396,-0.4135318116 N,1.4693173021,-0.0283039353,1.6313479543 C,0.8553745419,1.0854770168,1.6852808316 H,0.4885730815,1.3714747248,2.6775752275 C,-0.9363848119,-1.6968405195,0.4202349248 H,-0.7382110124,-2.200974495,1.3772452659 C,-2.3415294759,-1.315430145,0.1776917974 C,-5.014252955,-0.5981161147,-0.2067205635 C,-2.7334838221,-0.661990159,-0.9980765455 C,-3.2985001789,-1.6058458553,1.1543300358 C,-4.631066619,-1.2486817394,0.9637077187 C,-4.0630870129,-0.3062307422,-1.1870343417 H,-1.9887913054,-0.4438472261,-1.7575192582 H,-2.9922076021,-2.1124693592,2.0662070074 H,-5.3680930867,-1.4774877296,1.7271000004 H,-4.3629387673,0.1995856042,-2.0996995295 H,-6.0522992099,-0.3180078441,-0.3579615458 C,0.5748449789,2.1170180665,0.6474314302 C,0.0015831752,4.1893968201,-1.1483720082 C,0.1732430132,1.8266227678,-0.6627607151 C,0.6544114572,3.4557330372,1.0529631157 C,0.3860194904,4.4864803811,0.1584215272 C,-0.1135177512,2.8604134964,-1.5512171192 H,0.0605165047,0.7932028997,-0.9757556557 H,0.9342415638,3.6845002794,2.0784260307 H,0.4654024379,5.5193617529,0.4828714947 H,-0.4330069874,2.6244908121,-2.5618802202 H,-0.219346265,4.9911749502,-1.8463155643 E,E-(1)DMF (E,E-diimine 1 in DMF) cydiimph2_EE_dmf M062X/6-31G(d,p) E(RM062X) = -884.5337399 Zero-point correction= 0.379075 (Hartree/Particle) Thermal correction to Energy= 0.397991 Thermal correction to Enthalpy= 0.398935 Thermal correction to Gibbs Free Energy= 0.328306 Sum of electronic and ZPE= -884.154665 Sum of electronic and thermal Energies= -884.135749 149 Sum of electronic and thermal Enthalpies= -884.134805 Sum of electronic and thermal Free Energies= -884.205433 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 249.743 74.382 148.651 C,4.7758083554,-0.7039236572,0.2982286775 C,3.5130953552,-1.4644197849,-0.1060689076 C,2.2457544361,-0.7077373469,0.303008107 C,2.2457532623,0.7077414365,-0.3030082157 C,3.5130930344,1.4644258641,0.1060687017 C,4.7758072489,0.7039317212,-0.2982287951 H,3.4941738739,-1.6051555281,-1.1947607274 H,3.4923401261,-2.4605664669,0.3487650106 H,4.8223316118,-0.6327129703,1.3929881618 H,5.6633497247,-1.257782262,-0.0241224501 H,2.2208305426,0.5998210161,-1.401181193 H,3.4923362756,2.4605724835,-0.3487653114 H,3.4941713087,1.6051617172,1.1947604997 H,4.8223306725,0.6327211282,-1.3929882735 H,5.6633476825,1.2577917603,0.0241224298 H,2.2208316051,-0.5998169694,1.4011810928 N,1.0793330969,-1.4239110845,-0.1847473708 N,1.0793309061,1.4239133292,0.1847473417 C,0.2076720084,-1.7816133579,0.6670759781 H,0.3232237566,-1.5685815501,1.7399795277 C,0.2076690407,1.7816140952,-0.6670758597 H,0.3232209489,1.5685822017,-1.7399793944 C,-1.0216184252,-2.5087409661,0.2900774754 C,-1.9177791921,-2.8909236526,1.2919721517 C,-1.3064296337,-2.8215474628,-1.0451595345 C,-3.0849955263,-3.5789086151,0.9682410332 H,-1.695526321,-2.6466660483,2.3277597335 C,-2.4709282022,-3.5069210971,-1.3672160773 H,-0.6060743539,-2.5206186356,-1.8179945135 C,-3.3624042566,-3.8874939944,-0.3612939735 H,-3.7758028139,-3.8729668265,1.7521055104 H,-2.6883214189,-3.7468974879,-2.4034212 H,-4.2714796742,-4.423291235,-0.6165998773 C,-1.0216226585,2.5087394249,-0.290077287 C,-1.9177842163,2.8909203566,-1.2919718907 C,-1.3064343201,2.8215455747,1.0451597253 C,-3.0850018244,3.5789032373,-0.968240689 H,-1.6955311563,2.6466630879,-2.3277595127 C,-2.4709340643,3.5069171055,1.3672164082 150 H,-0.6060783207,2.520618116,1.8179945936 C,-3.3624108962,3.8874882224,0.3612942909 H,-3.7758097256,3.8729600519,-1.7521051363 H,-2.6883275747,3.7468932592,2.4034215128 H,-4.2714872984,4.4232838105,0.616600227 E,Z-(1)DMF (E,Z-diimine 1 in DMF) cydiimph2_ZE_dmf M062X/6-31G(d,p) E(RM062X) = -884.5260424 Zero-point correction= 0.379399 (Hartree/Particle) Thermal correction to Energy= 0.398083 Thermal correction to Enthalpy= 0.399027 Thermal correction to Gibbs Free Energy= 0.329614 Sum of electronic and ZPE= -884.146644 Sum of electronic and thermal Energies= -884.127960 Sum of electronic and thermal Enthalpies= -884.127016 Sum of electronic and thermal Free Energies= -884.196428 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 249.801 74.205 146.091 C,-0.5443266139,1.5753111893,1.0370017163 C,-0.6914767658,2.5272420542,3.3790439375 C,-1.0454354774,0.0657512136,2.9984489201 C,-1.430212594,1.2744859309,3.8507917715 C,-1.3043929524,0.318076085,1.5115629305 C,-0.9492938783,2.7809198243,1.8943993158 H,0.3860640126,2.3959363958,3.5444935779 H,0.021657552,-0.1583818514,3.1278614366 H,-2.5125427005,1.443277938,3.7743768331 H,-2.3789099661,0.5107230382,1.3490610407 H,-2.0161082602,2.9792070564,1.7274339898 H,0.5321965433,1.3969322818,1.1654289461 H,-1.0008663245,3.3990109944,3.9645654743 H,-1.6019349747,-0.8252317094,3.3085290088 H,-1.2117324599,1.0724770168,4.9043134174 H,-0.398450511,3.661294415,1.5462374127 N,-0.8547334937,-0.8272891306,0.7393609187 N,-0.9268214189,1.8579996677,-0.3373180722 C,-0.1027326728,1.8202906063,-1.3060514665 H,-0.503015407,2.127014266,-2.2789440541 C,-1.6255291228,-1.2680892397,-0.1697668868 H,-2.6169619281,-0.8283058525,-0.3517952536 151 C,-1.2471169945,-2.3868394439,-1.0558820531 C,-0.5767048253,-4.4779445998,-2.7827396345 C,-0.0246758716,-3.0558153145,-0.9107627376 C,-2.1284046744,-2.7765897359,-2.0683262593 C,-1.7946229748,-3.8184041705,-2.9303487327 C,0.3067088814,-4.0954684376,-1.7706139217 H,0.652412461,-2.755001788,-0.1170201725 H,-3.0768172106,-2.2568316548,-2.178648849 H,-2.4834475453,-4.1141258583,-3.7152926679 H,1.2545837867,-4.6118157694,-1.654664336 H,-0.3141743511,-5.2904384434,-3.4532152978 C,1.3446812018,1.4684215522,-1.3557041178 C,4.0717582932,0.8899626348,-1.6200409157 C,1.9044146328,0.3774730386,-0.6787369538 C,2.1598749252,2.2432076554,-2.1906161832 C,3.5181531155,1.9673102997,-2.3103465245 C,3.26096371,0.0921999083,-0.8147759051 H,1.2713052463,-0.2584227076,-0.0667286437 H,1.7212762451,3.0702455744,-2.7434086087 H,4.1416729825,2.5845766179,-2.9494956674 H,3.6843496601,-0.7603183539,-0.2924631306 H,5.1293687102,0.6659668163,-1.7192035819 E,E-(1)benzene (E,E-diimine 1 in benzene) cydiimph2_EE_benzene M062X/6-31G(d,p) E(RM062X) = -884.5340406 Zero-point correction= 0.379381 (Hartree/Particle) Thermal correction to Energy= 0.398259 Thermal correction to Enthalpy= 0.399203 Thermal correction to Gibbs Free Energy= 0.328976 Sum of electronic and ZPE= -884.154659 Sum of electronic and thermal Energies= -884.135782 Sum of electronic and thermal Enthalpies= -884.134838 Sum of electronic and thermal Free Energies= -884.205065 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 249.911 74.316 147.806 C,4.8218430184,-0.6944317495,0.3199343352 C,3.5600659875,-1.466265207,-0.064166903 C,2.2874966858,-0.7038073909,0.3163589062 C,2.2874955803,0.7038115769,-0.3163590086 C,3.5600637038,1.466271372,0.0641667662 152 C,4.8218419266,0.6944398789,-0.3199345104 H,3.5410573421,-1.6392431158,-1.1478514537 H,3.5384123657,-2.450508234,0.4153054796 H,4.8678782599,-0.5887280166,1.4120330382 H,5.7105129838,-1.2576833182,0.0177685927 H,2.2476421176,0.5683817978,-1.4116039015 H,3.5384085339,2.4505143655,-0.4153056148 H,3.5410548214,1.6392492511,1.1478513178 H,4.8678773006,0.5887362182,-1.4120332149 H,5.7105110226,1.2576928319,-0.017768794 H,2.2476430462,-0.5683776695,1.4116038016 N,1.1322726722,-1.4306412176,-0.17493245 N,1.1322704507,1.4306436157,0.1749323814 C,0.1838637736,-1.6621939259,0.635744264 H,0.226466141,-1.339338589,1.6872748235 C,0.1838611578,1.6621948319,-0.6357442981 H,0.2264639001,1.3393393661,-1.6872748035 C,-1.0462714162,-2.3720919649,0.2319761069 C,-2.0585737809,-2.5772545299,1.1716448705 C,-1.2145605793,-2.8410526649,-1.0761189427 C,-3.2278564587,-3.2426661352,0.8133130703 H,-1.9273125939,-2.2102228698,2.1864904054 C,-2.3803109836,-3.505087756,-1.4323318237 H,-0.4182948667,-2.6740380659,-1.794468075 C,-3.3893783563,-3.7071922464,-0.488676064 H,-4.0109929144,-3.3973205875,1.5486353456 H,-2.5075951045,-3.8681685257,-2.4474095522 H,-4.2998133746,-4.2267106824,-0.7709554744 C,-1.0462753475,2.3720904965,-0.2319759752 C,-2.0585782012,2.5772511715,-1.1716446296 C,-1.2145652676,2.8410508258,1.0761191055 C,-3.2278620956,3.2426605589,-0.8133126924 H,-1.9273164172,2.2102197934,-2.1864901887 C,-2.3803168946,3.5050837024,1.4323321284 H,-0.418299166,2.6740377185,1.7944681545 C,-3.3893847414,3.7071863162,0.488676479 H,-4.0109989191,3.3973135605,-1.54863488 H,-2.5076015953,3.8681641951,2.4474098821 H,-4.2998207168,4.2267030183,0.770955996 E,Z-(1)benzene (E,Z-diimine 1 in benzene) cydiimph2_ZE_benzene M062X/6-31G(d,p) E(RM062X) = -884.5266089 Zero-point correction= 0.379932 (Hartree/Particle) Thermal correction to Energy= 0.398551 153 Thermal correction to Enthalpy= 0.399495 Thermal correction to Gibbs Free Energy= 0.330768 Sum of electronic and ZPE= -884.146677 Sum of electronic and thermal Energies= -884.128058 Sum of electronic and thermal Enthalpies= -884.127114 Sum of electronic and thermal Free Energies= -884.195841 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 250.095 74.061 144.648 C,1.8104221567,-1.1158623515,0.3776759321 C,3.5278475406,-2.7314001161,-0.5502699796 C,1.116650754,-2.9263556859,-1.2427312222 C,2.4121841755,-3.6895764488,-0.9690484552 C,0.6878124248,-2.0901782884,-0.0344359439 C,3.1013562792,-1.8960373239,0.6566899801 H,3.7660608605,-2.0648375745,-1.3897597262 H,1.2516649008,-2.2491034601,-2.0959597681 H,2.2426208061,-4.4189531394,-0.1658332482 H,0.5068688153,-2.7520953119,0.8307069452 H,2.9278248085,-2.5451356027,1.5244747334 H,1.9883419223,-0.4228222071,-0.4566049622 H,4.4423947936,-3.2854789994,-0.3156771209 H,0.3039677315,-3.6117464945,-1.5053392588 H,2.7059819702,-4.2580692327,-1.8572239304 H,3.8860419049,-1.1867633953,0.9400232588 N,-0.5016857579,-1.3316368861,-0.3744851401 N,1.4155552038,-0.4560349669,1.6104676445 C,1.2348675736,0.7992703605,1.6921462074 H,1.0101658529,1.1776060776,2.6960920767 C,-1.4741355094,-1.3505020036,0.4414704594 H,-1.4343780174,-1.9334223963,1.3740944615 C,-2.7174238516,-0.5893630895,0.2100241361 C,-5.0792580063,0.8491093612,-0.1735487856 C,-2.9232638477,0.1222131252,-0.9779500372 C,-3.7053978833,-0.5784761183,1.1972531238 C,-4.8825180861,0.1400434138,1.008000871 C,-4.0980984292,0.837290234,-1.1664445749 H,-2.154216964,0.0949807786,-1.7434858415 H,-3.5455269262,-1.133541531,2.1181835048 H,-5.6442340013,0.1463238564,1.7810136066 H,-4.2546213904,1.3871071118,-2.0891860238 H,-5.9966560351,1.4094977193,-0.3241021499 C,1.3109335707,1.8729823693,0.6606321267 C,1.4609718095,4.0057354933,-1.1452882396 154 C,0.7509435643,1.7564134004,-0.6171284448 C,1.9158129273,3.0795224741,1.0314332495 C,2.0050261023,4.1350212251,0.1307841817 C,0.8272884465,2.8206613155,-1.511312731 H,0.2364613802,0.8407560634,-0.8953214605 H,2.323887072,3.1837459151,2.0336971361 H,2.4889770128,5.0604020241,0.4266555101 H,0.3834492889,2.7245115703,-2.4973665792 H,1.5201640564,4.8310397351,-1.8479305215 IA-E,E[1,1]MeOH (Intermediate monocoordinate 1,1-B2cat2-E,E-diimine 1 complex in MeOH) E-coord_cydiimph2_EE_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1559979 Zero-point correction= 0.570914 (Hartree/Particle) Thermal correction to Energy= 0.603263 Thermal correction to Enthalpy= 0.604207 Thermal correction to Gibbs Free Energy= 0.505323 Sum of electronic and ZPE= -1696.585084 Sum of electronic and thermal Energies= -1696.552735 Sum of electronic and thermal Enthalpies= -1696.551791 Sum of electronic and thermal Free Energies= -1696.650675 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.553 130.327 208.121 C,1.2402954659,-2.262922831,1.0735257707 C,1.5548442559,-4.7702872346,1.0136953087 C,-0.4584876179,-3.744713623,-0.1035864096 C,0.0813636177,-4.9638773372,0.6499879598 C,-0.2464961224,-2.4947589761,0.7488351816 C,1.7615841053,-3.4914663885,1.8277919457 H,2.1482248755,-4.7116764132,0.0914354157 H,0.068623585,-3.653348767,-1.0571780746 H,-0.503640772,-5.1145660106,1.5667428025 H,-0.7488708719,-2.6636949938,1.7085560122 H,1.2324921892,-3.5655603775,2.7869393303 H,1.8022826841,-2.1553450877,0.137456891 H,1.9241520585,-5.6327020175,1.5776603923 H,-1.5261333433,-3.8574085771,-0.3201924485 H,-0.0465396928,-5.8603348905,0.0355500077 H,2.822525771,-3.339236384,2.0518346361 N,-0.8805581901,-1.2846930488,0.1601246003 155 N,1.3565811697,-1.0763180257,1.9072908166 C,2.0733417588,-0.1273290887,1.457342897 C,-1.6730670594,-0.6420382894,0.9466335502 H,-1.7737518257,-1.0124240931,1.9681414996 H,2.5898440018,-0.2014724219,0.4889861016 C,-2.441310622,0.5754194426,0.6574722106 C,-3.7679528507,2.9952596671,0.256524287 C,-3.0902986248,0.8231399426,-0.5583696996 C,-2.5021265866,1.5266579949,1.6877697291 C,-3.1453009396,2.7400841748,1.4791650866 C,-3.7534413136,2.0326033437,-0.7507576897 H,-3.0827302321,0.0729295472,-1.3415483672 H,-2.0150618191,1.3192939919,2.6369456263 H,-3.1648446056,3.4846023946,2.2683882045 H,-4.2552404668,2.2231018812,-1.6940305781 H,-4.2748554324,3.9414373323,0.0938315351 C,2.2754667974,1.1408795719,2.1864974069 C,2.6979963888,3.5669546767,3.5065753253 C,3.1641377158,2.0842210105,1.6629099671 C,1.5857478118,1.4263169461,3.3708433488 C,1.7964730639,2.634202399,4.0258562729 C,3.3805687452,3.2913413292,2.323516731 H,3.6880510315,1.8652125504,0.7356617191 H,0.8903663155,0.6931299392,3.7681091899 H,1.2602509592,2.8517810409,4.944575399 H,4.0764651746,4.0166905277,1.9135738659 H,2.8629117369,4.50760964,4.0231825678 H,2.4090717632,-3.0098384664,-3.3491023394 C,1.3589517627,-2.9265742189,-3.6101849089 C,-1.4009048219,-2.701390693,-4.2552627871 C,0.5071512771,-2.1307677048,-2.8710653749 C,0.8099250961,-3.6194537353,-4.7040841027 C,-0.5392629878,-3.5086775119,-5.0192940688 C,-0.8527996552,-2.0187950623,-3.1878749766 H,1.454516116,-4.2497739099,-5.3084815971 H,-0.9401947535,-4.0538071663,-5.8680119155 H,-2.4561846951,-2.6103706801,-4.4909134056 O,-1.4762707552,-1.1827599799,-2.3161954544 O,0.8018066756,-1.3836661091,-1.7738624158 B,-0.4507660519,-0.7240236341,-1.3412262185 H,0.6710579717,3.8598190846,1.5728313888 C,0.253245593,4.0250618291,0.5843105217 C,-0.8923731046,4.4067762352,-2.0110616782 C,0.0248156162,2.9744714301,-0.2819648171 C,-0.1080170032,5.2973459439,0.1231637148 C,-0.665198933,5.4834032005,-1.1438764969 156 C,-0.5352852477,3.1574994697,-1.5436232792 H,0.0448031507,6.1562548096,0.7685490759 H,-0.9351071921,6.4843436468,-1.4644490354 H,-1.3353675217,4.5392430653,-2.9920275388 O,-0.6893379422,1.9310972505,-2.1472782396 O,0.2357913619,1.6354004795,-0.0787212906 B,-0.2779480491,0.9824879096,-1.2045590755 IA-E,Z[1,1]MeOH (Intermediate monocoordinate E-coordinated 1,1-B2cat2-E,Z-diimine 1 complex in MeOH) E-coord_cydiimph2_EZ_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1438106 Zero-point correction= 0.571186 (Hartree/Particle) Thermal correction to Energy= 0.603542 Thermal correction to Enthalpy= 0.604487 Thermal correction to Gibbs Free Energy= 0.504487 Sum of electronic and ZPE= -1696.572624 Sum of electronic and thermal Energies= -1696.540268 Sum of electronic and thermal Enthalpies= -1696.539324 Sum of electronic and thermal Free Energies= -1696.639324 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.729 130.167 210.467 C,0.7536247194,-1.8416011395,1.539131324 C,1.1653540738,-4.341336494,1.4949019718 C,-0.8324510113,-3.3993540206,0.2860629753 C,-0.2870453345,-4.5887473325,1.0820105052 C,-0.699849099,-2.134947071,1.1311378268 C,1.2986157481,-3.0531699849,2.3087786128 H,1.7882263721,-4.2672641898,0.5935847075 H,-0.2652459549,-3.3082792319,-0.642743141 H,-0.9003345566,-4.7436286123,1.9794328917 H,-1.2488265077,-2.3079873732,2.0643130216 H,0.7425750989,-3.1451081247,3.2510187626 H,1.3582341273,-1.6975257309,0.6408818024 H,1.5452505968,-5.1860614134,2.0784145579 H,-1.8850629407,-3.5502657326,0.0236491015 H,-0.3629950277,-5.4986778322,0.4789041111 H,2.3454154714,-2.857124219,2.5653976341 N,-1.3151302268,-0.9307086835,0.5129995219 N,0.7367985769,-0.689516975,2.4339367639 C,1.6825781913,0.1609826496,2.4508202744 157 C,-2.0831009977,-0.2508433136,1.2921143015 H,-2.2175859899,-0.6227064519,2.3081346302 H,1.6069968633,0.9394323067,3.2180302713 C,-2.7619147183,1.0198442985,1.0073419819 C,-3.881135306,3.545122177,0.6294684477 C,-3.3893669939,1.3304235097,-0.2048666805 C,-2.7407418519,1.9641395992,2.0456048999 C,-3.2789455144,3.2292555992,1.848236225 C,-3.9500656695,2.592661787,-0.3850220907 H,-3.44256702,0.5902846521,-0.9957525952 H,-2.2715077691,1.7068840046,2.9916803601 H,-3.2338068369,3.9664252856,2.6432424613 H,-4.4358715578,2.8324394571,-1.3254469074 H,-4.3064032467,4.5319970216,0.4750073604 C,2.9241139131,0.2484436579,1.6293929944 C,5.3273470716,0.500264808,0.2178824387 C,4.1306965392,0.4472369618,2.3107312015 C,2.9279088562,0.2068099334,0.2304861455 C,4.125805711,0.3333210326,-0.4684173555 C,5.3282605233,0.5581988006,1.6104286281 H,4.1262711137,0.5096902365,3.3960751117 H,1.9966007814,0.0910100729,-0.3144694628 H,4.117889951,0.3055906031,-1.5537696215 H,6.259390733,0.6990191663,2.150506783 H,6.2589847214,0.595960654,-0.3313085326 H,1.8270228358,-2.8444925744,-3.0337866641 C,0.7832783297,-2.6877994523,-3.2868875143 C,-1.9577193212,-2.2644509638,-3.9112621055 C,-0.008287071,-1.846800652,-2.5311567453 C,0.1827278871,-3.3249615159,-4.3873799991 C,-1.1575076225,-3.1171760053,-4.6922954043 C,-1.3590377998,-1.637833691,-2.8363134617 H,0.7794696533,-3.9887171938,-5.0049811912 H,-1.5992570307,-3.6199544855,-5.5468671306 H,-3.0050799736,-2.0965901698,-4.1399263773 O,-1.9177730822,-0.7703695991,-1.9521490632 O,0.345068029,-1.1351237812,-1.4276025405 B,-0.8567051612,-0.3921850798,-0.9790892569 H,0.7027100835,4.214869813,1.7562388784 C,0.2551725532,4.366585215,0.7799550136 C,-0.9428019071,4.7278595927,-1.7922917651 C,-0.0947050754,3.2997434935,-0.0235724567 C,-0.0110761361,5.6433252833,0.2694018076 C,-0.5964586881,5.8195599604,-0.9859882463 C,-0.6759788406,3.4750672369,-1.2766787415 H,0.2411989613,6.5138097596,0.8661353221 158 H,-0.7909798237,6.8243347265,-1.3465677121 H,-1.4031600924,4.8522025617,-2.7663042585 O,-0.9396048955,2.2423969589,-1.824736774 O,0.013890636,1.9551914784,0.2341910643 B,-0.571392051,1.3009247454,-0.8580288692 IA-Z,E[1,1]MeOH (Intermediate monocoordinate Z-coordinated 1,1-B2cat2-Z,E-diimine 1 complex in MeOH) Z-coord_cydiimph2_ZE_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1589768 Zero-point correction= 0.571378 (Hartree/Particle) Thermal correction to Energy= 0.603524 Thermal correction to Enthalpy= 0.604468 Thermal correction to Gibbs Free Energy= 0.506387 Sum of electronic and ZPE= -1696.587599 Sum of electronic and thermal Energies= -1696.555453 Sum of electronic and thermal Enthalpies= -1696.554509 Sum of electronic and thermal Free Energies= -1696.652590 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.717 130.042 206.429 C,1.2608790525,-1.3550448511,0.2933484786 C,2.1934755154,-3.7190508635,0.1759370656 C,-0.0720306704,-3.2399513067,-0.7942134506 C,0.7908060255,-4.2754943107,-0.072602626 C,-0.1293846184,-1.9548829968,0.0356102359 C,2.1348494277,-2.4182256956,0.9763939439 H,2.6825906474,-3.5314173452,-0.788842525 H,0.3593162977,-3.0273805251,-1.7762206696 H,0.3255173154,-4.5388069341,0.8868698915 H,-0.5273198328,-2.1959780093,1.0255757477 H,1.7179952195,-2.6124910327,1.9735936755 H,1.7331922054,-1.0571594024,-0.6550994434 H,2.8073461491,-4.4508288656,0.7106367256 H,-1.0892230655,-3.6134962635,-0.9559592514 H,0.8419243585,-5.1918776562,-0.6685613449 H,3.1362061739,-1.99856415,1.1199229172 N,-1.0177343001,-0.9407309688,-0.5647192622 N,1.0965991467,-0.2176812674,1.1919076605 C,1.9903410954,0.6874707274,1.167988164 C,-2.1243389175,-0.5843603222,-0.0195104676 H,-2.6285937987,0.252990805,-0.5032782347 159 H,2.8485446377,0.6461400429,0.4800820937 C,-2.7957156131,-1.1130425006,1.1772374254 C,-4.1721828703,-1.9319630567,3.461137145 C,-3.4190510466,-0.1679597424,2.0034137915 C,-2.8994407204,-2.4770389462,1.4826832125 C,-3.5913948866,-2.8798568677,2.6193344859 C,-4.0855830352,-0.5754022971,3.153272503 H,-3.3650347121,0.8859540797,1.7442604274 H,-2.4718175677,-3.2225960477,0.8198822222 H,-3.6801323612,-3.9372598235,2.8461259548 H,-4.5488817008,0.1628263723,3.7995853361 H,-4.7053073355,-2.2528254386,4.3506173642 C,1.9385188322,1.8560564168,2.0686179692 C,1.8688464598,4.1025061475,3.723765861 C,3.0195015297,2.7408207435,2.0996983539 C,0.8161242185,2.1039371351,2.8697541704 C,0.7838671459,3.2225775469,3.6923992432 C,2.9865674677,3.8603358579,2.9284676307 H,3.8835778804,2.5506093716,1.4675043066 H,-0.0255409285,1.4191547777,2.8268603855 H,-0.0887531864,3.4162305343,4.3088586713 H,3.8280305911,4.5461902591,2.9462473697 H,1.838440758,4.9779020761,4.3654190463 H,0.8023397249,-2.8367659504,-4.6328399519 C,-0.1699471692,-2.3544993153,-4.6236311201 C,-2.7043599227,-1.0661288533,-4.5789081065 C,-0.4675819917,-1.3798841213,-3.6913702325 C,-1.1697463227,-2.6867966859,-5.5533320917 C,-2.4093807429,-2.056176318,-5.5312955115 C,-1.7175745618,-0.7466634237,-3.6666811008 H,-0.9673787403,-3.4498442522,-6.2982908116 H,-3.1657265726,-2.3315802247,-6.259512069 H,-3.6677381263,-0.5674571106,-4.5534954595 O,-1.7599306013,0.1834417347,-2.6717353742 O,0.3376676792,-0.8814888643,-2.7116092104 B,-0.5333702266,-0.044468754,-1.8675610878 H,3.5261404651,3.7509855843,-1.9061809126 C,2.6631322805,3.9886854544,-1.2939264295 C,0.3715483427,4.5837305403,0.3124628173 C,1.6007945069,3.1136589621,-1.175818401 C,2.5608625388,5.1897654077,-0.5818924366 C,1.4416445147,5.4797562234,0.2026834417 C,0.4858300907,3.4026562293,-0.3950202338 H,3.3705475157,5.9097941277,-0.6412071824 H,1.4000172015,6.419344534,0.7443837714 H,-0.4988440737,4.7948712779,0.9241543586 160 O,-0.3959336853,2.3494205,-0.4665666427 O,1.4323805838,1.8768758279,-1.7551331409 B,0.1890102892,1.4084320833,-1.3216790923 IA-Z,Z[1,1]MeOH (Intermediate monocoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in MeOH) Z-coord_cydiimph2_ZZ_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1477281 Zero-point correction= 0.571986 (Hartree/Particle) Thermal correction to Energy= 0.603999 Thermal correction to Enthalpy= 0.604943 Thermal correction to Gibbs Free Energy= 0.506545 Sum of electronic and ZPE= -1696.575742 Sum of electronic and thermal Energies= -1696.543729 Sum of electronic and thermal Enthalpies= -1696.542785 Sum of electronic and thermal Free Energies= -1696.641183 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.015 129.755 207.095 C,0.739556113,-0.9657236895,0.7253394913 C,1.763220777,-3.2892217534,0.7104532809 C,-0.4702483469,-2.9189622436,-0.3850679353 C,0.400263653,-3.9065496569,0.3941396092 C,-0.6161292143,-1.6220397939,0.4199459906 C,1.6043049664,-1.9825027727,1.4869757894 H,2.2999109513,-3.092151604,-0.2272714446 H,-0.0082653495,-2.7130681935,-1.3531371166 H,-0.1004395494,-4.1809112486,1.3319646818 H,-1.063162549,-1.8864355832,1.379981009 H,1.1138674447,-2.1798183182,2.4494886448 H,1.2188116793,-0.703295587,-0.2278370408 H,2.3748092635,-3.9881586496,1.2899008534 H,-1.4675241212,-3.3328530432,-0.5701318044 H,0.5212349626,-4.8257036923,-0.1875432953 H,2.5786471203,-1.5372689739,1.7095623844 N,-1.5235125416,-0.6723402796,-0.2589116415 N,0.4803319874,0.2027061239,1.5566485726 C,1.3348187451,1.1126569687,1.818516456 C,-2.6886627583,-0.3913160742,0.1998504114 H,-3.2923781692,0.2514011925,-0.4411173657 H,0.9664068994,1.8901990775,2.4970119573 C,-3.3280845732,-0.8279988243,1.4548980564 161 C,-4.695621012,-1.5645868985,3.769590269 C,-2.6953369216,-0.73232683,2.7012979495 C,-4.6592334645,-1.2552697101,1.3790784518 C,-5.3326578946,-1.6436084968,2.5322536955 C,-3.3847325735,-1.0971878467,3.8530596584 H,-1.6800029864,-0.3492706233,2.7589761275 H,-5.157007194,-1.2917323548,0.4140040365 H,-6.3577383969,-1.9936261296,2.4666042303 H,-2.8973230026,-1.013022926,4.8190836224 H,-5.2256841738,-1.8544386295,4.6715425788 C,2.7393211782,1.3718837957,1.4121170809 C,5.3629671706,2.1505082243,0.7785370638 C,3.3451780437,2.4639157177,2.0522904479 C,3.4763624657,0.6716736221,0.4425695568 C,4.7727108182,1.066807997,0.1281906068 C,4.6470059543,2.846796371,1.7490258124 H,2.7782281122,3.0225844502,2.7930831709 H,3.0566933469,-0.1776810268,-0.0801942294 H,5.3269196984,0.5208764339,-0.6288951473 H,5.0952950137,3.693555572,2.2593369927 H,6.3767872756,2.4478630412,0.5287718073 H,0.1799628898,-2.7653879799,-4.2703442021 C,-0.7721357368,-2.2443603232,-4.2687847691 C,-3.2526435572,-0.8529247766,-4.2480054075 C,-1.0192145121,-1.2232533708,-3.3722035771 C,-1.7957116028,-2.570961921,-5.1742437593 C,-3.0085150383,-1.8896746279,-5.1645749809 C,-2.2432003756,-0.540386577,-3.3589352142 H,-1.6330864553,-3.3695527259,-5.8911730344 H,-3.7835148733,-2.161611945,-5.8742335383 H,-4.194646426,-0.314509289,-4.2324435923 O,-2.2363721689,0.4276661934,-2.3984474092 O,-0.1830283195,-0.7152409261,-2.4244010905 B,-1.0191368572,0.1713456529,-1.5956156868 H,3.404473688,3.4992338451,-1.6764970745 C,2.5750450924,3.8437830583,-1.0682572591 C,0.3799674607,4.7051777644,0.5528852927 C,1.4142549372,3.1056554527,-0.9494840696 C,2.6253813443,5.0410159033,-0.3447205511 C,1.555941074,5.4587130969,0.4515660077 C,0.3403268704,3.5294824326,-0.1718642676 H,3.5203401761,5.6527249684,-0.3979843092 H,1.6344484818,6.3901651355,1.0026917783 H,-0.4586222725,5.022235167,1.1630042817 O,-0.6720464145,2.6022886784,-0.2614128393 O,1.1032304129,1.8928645087,-1.5149282005 162 B,-0.1914066555,1.581155451,-1.0855758442 IA-E,E[1,2]MeOH (Intermediate monocoordinate 1,2-B2cat2-E,E-diimine 1 complex in MeOH) maxstep10_E-coord_cydiimph2_EE_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1570579 Zero-point correction= 0.571338 (Hartree/Particle) Thermal correction to Energy= 0.603306 Thermal correction to Enthalpy= 0.604250 Thermal correction to Gibbs Free Energy= 0.507496 Sum of electronic and ZPE= -1696.585720 Sum of electronic and thermal Energies= -1696.553752 Sum of electronic and thermal Enthalpies= -1696.552808 Sum of electronic and thermal Free Energies= -1696.649562 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.580 130.247 203.636 C,-0.0845035025,-2.0933833084,-1.1097854102 C,1.4729593125,-3.8994453931,-1.9694065761 C,2.3072078269,-1.5362003686,-1.736124441 C,2.4079179803,-2.8331860288,-2.5430585588 C,0.8587988913,-1.0552277138,-1.7355251404 C,0.0289866184,-3.3993433307,-1.9088500362 H,1.8064004191,-4.162604059,-0.9569392441 H,2.6399821188,-1.7381164463,-0.7127761949 H,2.1403683357,-2.6340322172,-3.5888502239 H,0.5472735926,-0.9422106283,-2.7799842511 H,-0.3500335666,-3.2161633841,-2.9228677665 H,0.2163568934,-2.2929933874,-0.0688591916 H,1.5216869249,-4.8130250246,-2.5702849942 H,2.9559714445,-0.7575181942,-2.1511748001 H,3.4425756387,-3.1889645832,-2.53660854 H,-0.6249040108,-4.1462302182,-1.4464333801 N,-1.4440643132,-1.5782305072,-1.1699725444 N,0.6917736866,0.2762459113,-1.0998986254 C,-0.1011174228,1.0810390708,-1.7212563617 H,-0.6004507203,0.6837782463,-2.6059591375 C,-2.2453559529,-1.9606178737,-0.2605219705 H,-1.936952203,-2.661825806,0.5287634247 B,1.3655369774,0.5492100095,0.362622655 B,1.6075916811,-0.7407244131,1.4320599566 O,2.8689353839,-1.1861580387,1.7559676137 163 O,0.4542214279,1.438407835,1.1021156544 C,3.8179958212,0.5913506547,0.3651124957 C,6.3313391792,-0.6189434617,0.7418901491 C,3.9443215884,-0.5869029321,1.1307892993 C,4.9738214723,1.1397175833,-0.1949318729 C,6.219567446,0.5480564158,-0.0095724541 C,5.1894928775,-1.1786769736,1.3079043669 H,4.8642372628,2.0466991647,-0.7819590348 H,7.0986948151,0.9996726916,-0.4580244779 H,5.2386160838,-2.084711555,1.9042954816 H,7.2960395165,-1.0921958865,0.8909720922 O,2.6427593312,1.2317578816,0.139254571 C,-0.6311443671,0.8462363635,1.6652194234 C,-2.8791549512,-0.2579080628,2.9336670334 C,-0.5679140736,-0.4319045732,2.2592515312 C,-1.8428488345,1.5386216893,1.6991612311 C,-2.9589125041,0.9961523339,2.3336693976 C,-1.6820162347,-0.970072506,2.8914778948 H,-1.8781806906,2.5215531195,1.2365457087 H,-3.8903234937,1.5535497523,2.3513095915 H,-1.587589779,-1.9491845165,3.3519953755 H,-3.7443096296,-0.6881155212,3.427599725 O,0.6140627813,-1.1412094284,2.3023793379 C,-0.4272945729,2.4772711032,-1.4223897219 C,-1.2007659179,5.1179202652,-0.9803610312 C,0.4849613448,3.3912634608,-0.8782161782 C,-1.7098336003,2.907751945,-1.7877441478 C,-2.1043975423,4.2188711743,-1.5432097599 C,0.0960932407,4.7070858278,-0.6657252182 H,1.4931588177,3.0720575058,-0.6387574742 H,-2.3992193236,2.2063497779,-2.2502624082 H,-3.1068976561,4.5409297581,-1.8051131763 H,0.8051437653,5.4169018832,-0.2522046614 H,-1.4999638232,6.1462422001,-0.8020067926 C,-3.6402554737,-1.4857389981,-0.188513459 C,-6.2555353234,-0.5439316184,0.0640847119 C,-4.5388169566,-2.1256688909,0.6691531446 C,-4.0574893495,-0.3661703951,-0.9170185381 C,-5.3593594595,0.1031170024,-0.789248434 C,-5.8456820164,-1.6607326265,0.7902547863 H,-4.2050515444,-2.9836210072,1.2480619922 H,-3.3445800914,0.1361433462,-1.5640207886 H,-5.6768993826,0.9782146205,-1.3481038767 H,-6.5406590783,-2.1629341591,1.4560230622 H,-7.2710981355,-0.1735005561,0.1655961872 164 IA-E,Z[1,2]MeOH (Intermediate monocoordinate E-coordinated 1,2-B2cat2-E,Z-diimine 1 complex in MeOH) E-coord_cydiimph2_EZ_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1478526 Zero-point correction= 0.572175 (Hartree/Particle) Thermal correction to Energy= 0.603913 Thermal correction to Enthalpy= 0.604858 Thermal correction to Gibbs Free Energy= 0.508682 Sum of electronic and ZPE= -1696.575678 Sum of electronic and thermal Energies= -1696.543939 Sum of electronic and thermal Enthalpies= -1696.542995 Sum of electronic and thermal Free Energies= -1696.639170 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.961 129.897 202.418 C,-1.5609800952,-1.1722612787,0.2720604665 C,-3.1701198155,-1.2598478526,2.2357070819 C,-0.7107398629,-0.9521119906,2.6519935812 C,-2.0113050918,-1.5516763122,3.1895717394 C,-0.4237209323,-1.4987960339,1.2549547615 C,-2.8606559802,-1.7760421004,0.8313476943 H,-3.343483632,-0.1757531642,2.1956362529 H,-0.8259279356,0.1356792597,2.6123938528 H,-1.8961023345,-2.6374154956,3.3027627954 H,-0.3690741019,-2.5907273628,1.3223671192 H,-2.7366649322,-2.8664502734,0.8545198761 H,-1.6530597719,-0.0805986786,0.2030251281 H,-4.0933787306,-1.7194011781,2.6023757688 H,0.1336228179,-1.1722239327,3.313794348 H,-2.218261471,-1.1431373719,4.1832887984 H,-3.6843066574,-1.5653313184,0.1421111165 N,-1.2512734039,-1.7758886953,-1.0111896181 N,0.8881523651,-1.0386108349,0.7343380915 C,1.5856560925,-1.9414906626,0.1352893386 H,1.1185283054,-2.9198909462,0.0190461627 C,-1.7781557903,-1.387794406,-2.104891853 H,-1.4610146018,-1.9544528821,-2.9868623685 B,1.2611033864,0.5496195246,0.8377281118 B,0.0222418809,1.6982398196,0.7459078754 O,-0.3104129331,2.4919675646,1.8197093918 O,2.1107607104,0.8854438866,-0.3166123849 C,1.5081839596,1.4627888371,3.1026515928 165 C,0.5710353868,2.8916789466,5.3406932324 C,0.3757264107,2.2990249896,3.002900164 C,2.1491143237,1.3687344886,4.3400923343 C,1.6933154898,2.074501756,5.4490493202 C,-0.0803182054,2.9970765255,4.1153294677 H,3.0185043565,0.7212428069,4.4044635701 H,2.2154640438,1.9793585699,6.3957536547 H,-0.9552619782,3.628075187,3.9914589135 H,0.202928157,3.4450857903,6.1980668831 O,2.0190475379,0.7368694795,2.0760709548 C,1.4694326825,1.0489048472,-1.5023036205 C,0.2450238509,1.4355242716,-3.9966910846 C,0.1994312486,1.6586887407,-1.5943557999 C,2.0997730785,0.63469765,-2.6761561155 C,1.4945477131,0.8261473502,-3.9163498877 C,-0.3950237913,1.858016661,-2.833231906 H,3.0790490883,0.1712932589,-2.589222556 H,2.0029832924,0.4973784239,-4.8172480875 H,-1.3680616389,2.3411835588,-2.8656924981 H,-0.2350645741,1.5882822196,-4.9580777181 O,-0.4406035991,2.1492451284,-0.4743778502 C,2.9432084598,-1.8489949462,-0.4076266955 C,5.4904123994,-1.8349510868,-1.5339531365 C,3.9683043755,-1.1078068196,0.1941756093 C,3.2128096143,-2.6155998992,-1.5484943998 C,4.4783638016,-2.5894087085,-2.1247313423 C,5.2380648104,-1.1090890377,-0.3681934286 H,3.7687010804,-0.5464889193,1.1008574189 H,2.4201175879,-3.2134527186,-1.9904218187 H,4.677582774,-3.1655195359,-3.022358429 H,6.0352074125,-0.5420023594,0.1014526546 H,6.4835347395,-1.8239768127,-1.9725521708 C,-2.7213022955,-0.2987426399,-2.4697949922 C,-4.3257635277,1.77873299,-3.4842195668 C,-2.8891102333,-0.116624731,-3.852002952 C,-3.4013311786,0.5708274523,-1.6003167617 C,-4.1905431236,1.5992373423,-2.1089941895 C,-3.6767033991,0.909393537,-4.359021136 H,-2.3719228838,-0.7840605626,-4.5366007713 H,-3.3421764942,0.4635003157,-0.5258569542 H,-4.7052905081,2.2628367227,-1.4213068314 H,-3.7819027396,1.0318830661,-5.4324481066 H,-4.9409150091,2.5854605602,-3.8707881016 166 IA-Z,E[1,2]MeOH (Intermediate monocoordinate Z-coordinated 1,2-B2cat2-Z,E-diimine 1 complex in MeOH) Z-coord_cydiimph2_ZE_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.156959 Zero-point correction= 0.571411 (Hartree/Particle) Thermal correction to Energy= 0.603490 Thermal correction to Enthalpy= 0.604434 Thermal correction to Gibbs Free Energy= 0.506137 Sum of electronic and ZPE= -1696.585548 Sum of electronic and thermal Energies= -1696.553469 Sum of electronic and thermal Enthalpies= -1696.552525 Sum of electronic and thermal Free Energies= -1696.650822 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.696 130.173 206.884 C,-1.5567213401,-0.2354493869,0.1456858385 C,-3.4279349389,-0.0413695197,1.8598438944 C,-1.068160055,0.4268374766,2.5714126186 C,-2.4158422079,-0.15412833,2.999989439 C,-0.5655032667,-0.291419907,1.3202775277 C,-2.9222708984,-0.7622837143,0.6112202736 H,-3.5955273756,1.0191547589,1.6293240498 H,-1.1999981714,1.4951052307,2.3711251199 H,-2.2912609548,-1.2091523124,3.2771815061 H,-0.4522887293,-1.3516357143,1.5541404141 H,-2.8185622399,-1.8352682686,0.8193458482 H,-1.6725391253,0.803283322,-0.2062100364 H,-4.393092067,-0.4611711307,2.1602453198 H,-0.3197900056,0.3322776045,3.366441567 H,-2.7751544326,0.3737763631,3.8884250871 H,-3.6288409902,-0.6601945264,-0.2191426405 N,-1.0499064932,-1.1108003683,-0.9002004118 N,0.7392765215,0.2242454046,0.8639530569 C,1.7406427299,-0.5447331445,0.6360537111 H,2.6034744417,-0.0631670403,0.1725595899 C,-1.2143564689,-0.7598272514,-2.1107845291 H,-1.6947605882,0.19091534,-2.3880071939 B,1.004140809,1.8096270389,0.5216267012 B,-0.2264686556,2.9567070333,0.6197001461 O,-0.3693352194,3.7509384694,1.7361674884 O,1.5400560474,1.8527705871,-0.8421978607 C,1.6702750585,2.7527513966,2.6365114409 167 C,0.9588998915,3.8147601266,5.1412013921 C,0.4757810705,3.4887327537,2.7968656019 C,2.4890460868,2.5705924309,3.7517636285 C,2.1437417806,3.0985330385,4.9930888952 C,0.1296614595,4.0059781973,4.0387095948 H,3.4053963048,2.0040466084,3.6162569378 H,2.8005098694,2.9422063277,5.8429030145 H,-0.7983873445,4.564018385,4.1175583878 H,0.6782960822,4.2260278974,6.1050844192 O,2.066924095,2.2327752952,1.4447316579 C,0.6629965236,2.0732937425,-1.8557039761 C,-1.0407301758,2.5212809754,-4.0496207298 C,-0.5351363317,2.8062952859,-1.7030216181 C,0.9802820684,1.583431359,-3.1238190544 C,0.1448899248,1.8088648858,-4.2140047194 C,-1.3732923636,3.0176038334,-2.7912651844 H,1.9037361601,1.0216854716,-3.2294876971 H,0.4181628423,1.4150600368,-5.1879696252 H,-2.2820128313,3.5895164536,-2.6293766815 H,-1.7013982424,2.6982230087,-4.892022862 O,-0.8953190872,3.3868032515,-0.5031597147 C,1.8806399621,-1.9864632381,0.8994168027 C,2.2767600485,-4.7149909731,1.2991472409 C,1.5523309958,-2.5673023274,2.1305631119 C,2.4471854437,-2.7690919797,-0.1136932402 C,2.6211704573,-4.1357766911,0.0789237258 C,1.7572800687,-3.9285857856,2.3269547051 H,1.163984218,-1.9512811606,2.9368357117 H,2.7324407333,-2.3047596277,-1.0539828128 H,3.0389780137,-4.7440712503,-0.7168406495 H,1.5125866427,-4.3758593103,3.2848425847 H,2.4258688325,-5.7788475385,1.4550132976 C,-0.787564826,-1.622829993,-3.2322166836 C,-0.0064006216,-3.2271454747,-5.3821811083 C,-1.1595903054,-1.2850846978,-4.5364351631 C,-0.0229875687,-2.7751084832,-3.0105430855 C,0.3675058971,-3.5701161205,-4.0809668015 C,-0.7732535973,-2.0863058667,-5.6084274075 H,-1.7543731427,-0.3911179011,-4.7058961991 H,0.2595235784,-3.0341781483,-1.9945870823 H,0.9649535393,-4.4594402776,-3.9039707929 H,-1.06883144,-1.8192246144,-6.6182882813 H,0.300193884,-3.8499372762,-6.2170674658 168 IA-Z,Z[1,2]MeOH (Intermediate monocoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in MeOH) Z-coord_cydiimph2_ZZ_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1468077 Zero-point correction= 0.572266 (Hartree/Particle) Thermal correction to Energy= 0.604005 Thermal correction to Enthalpy= 0.604950 Thermal correction to Gibbs Free Energy= 0.509002 Sum of electronic and ZPE= -1696.574542 Sum of electronic and thermal Energies= -1696.542802 Sum of electronic and thermal Enthalpies= -1696.541858 Sum of electronic and thermal Free Energies= -1696.637806 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.019 129.782 201.940 C,-1.0862819239,-0.8124306646,0.1552275463 C,-2.7323836889,-0.9720045353,2.0796452565 C,-0.3174759384,-0.4498947793,2.5458722993 C,-1.5798611663,-1.1340783116,3.0717717606 C,0.0486396392,-1.0158239583,1.1761979845 C,-2.3454330562,-1.5053597505,0.7008342688 H,-2.9935026484,0.0919710562,1.9976965399 H,-0.5129984816,0.6251593759,2.4604302102 H,-1.3791133456,-2.2022162149,3.2268215413 H,0.1922311821,-2.093876115,1.2629499414 H,-2.134041119,-2.580690185,0.7620501618 H,-1.266723958,0.2657776262,0.0530374782 H,-3.6239182638,-1.4945179251,2.4404201621 H,0.5241735267,-0.5778252098,3.2354265414 H,-1.8479586072,-0.7110582826,4.0445842721 H,-3.1649092597,-1.3825590262,-0.0142684393 N,-0.6845596979,-1.4209781653,-1.100558677 N,1.2888769242,-0.4222802207,0.6448590033 C,2.2224487442,-1.1465197008,0.1444931448 H,3.0299361754,-0.5950254377,-0.3370721045 C,-1.217642088,-1.123198191,-2.2192401465 H,-0.8208858459,-1.6849418903,-3.0718652811 B,1.5059141124,1.1999114557,0.6459285035 B,0.2051428306,2.2523428141,0.4399688294 O,-0.2383129133,3.0653122446,1.456687088 O,2.3968989388,1.4840802486,-0.4943502023 C,1.6022552348,2.2470461866,2.8582092061 169 C,0.4791742829,3.7253706072,4.9759216604 C,0.4152195746,2.9884818426,2.6719257851 C,2.2011154014,2.2718600405,4.119897243 C,1.6538781209,3.0031406237,5.1693534809 C,-0.1317173946,3.711992842,3.7254972786 H,3.1126047044,1.6964924823,4.2512004206 H,2.145997044,3.0015868308,6.1367011287 H,-1.0451318332,4.2675712867,3.5356717823 H,0.0394873146,4.2970751657,5.7862502997 O,2.2025118781,1.5024627124,1.8951845221 C,1.7782100266,1.5284893966,-1.7076097072 C,0.6051300998,1.6486361751,-4.2553503637 C,0.4830750735,2.0656300485,-1.8798992451 C,2.4536610453,1.0446805983,-2.8278559034 C,1.8760100995,1.1037757242,-4.0943387313 C,-0.0837818903,2.1334974253,-3.1457636105 H,3.4479662349,0.632588157,-2.6819451355 H,2.422548253,0.7226668661,-4.9511084189 H,-1.0789242355,2.5604927926,-3.2396729023 H,0.1445535825,1.6988822481,-5.2368052758 O,-0.2259000314,2.600726928,-0.8235651215 C,2.3464577745,-2.6151597846,0.1359353486 C,2.7284524957,-5.3715958815,0.0133086227 C,2.2332418633,-3.388093158,1.2973085689 C,2.6844667196,-3.2224592567,-1.0783667547 C,2.8541996404,-4.6013014388,-1.1417485801 C,2.4299642582,-4.7635580094,1.2319162895 H,2.015894701,-2.9108690019,2.2488969666 H,2.7974703551,-2.6099846336,-1.969072114 H,3.0964694597,-5.0725465974,-2.0887443589 H,2.3517340721,-5.3607880618,2.1345720085 H,2.874144263,-6.4462651231,-0.0336010305 C,-2.2566959182,-0.1497523542,-2.6461649955 C,-4.0404020989,1.7115105159,-3.7758080782 C,-2.4351078328,-0.0625935232,-4.0364341372 C,-3.0162399405,0.7030467969,-1.8272666693 C,-3.893218605,1.6251849817,-2.3929506472 C,-3.3122661992,0.8555230833,-4.6001609366 H,-1.8560869393,-0.7167833999,-4.68327279 H,-2.9508307287,0.6648443394,-0.7484835807 H,-4.4677559859,2.2783809796,-1.7437326851 H,-3.4249208765,0.9055967898,-5.6785901804 H,-4.725173115,2.4352394701,-4.2069863113 170 IA-E,E[1,1]DMF (Intermediate monocoordinate 1,1-B2cat2-E,E-diimine 1 complex in DMF) E-coord_cydiimph2_EE_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1542304 Zero-point correction= 0.571476 (Hartree/Particle) Thermal correction to Energy= 0.603768 Thermal correction to Enthalpy= 0.604712 Thermal correction to Gibbs Free Energy= 0.505815 Sum of electronic and ZPE= -1696.582754 Sum of electronic and thermal Energies= -1696.550463 Sum of electronic and thermal Enthalpies= -1696.549518 Sum of electronic and thermal Free Energies= -1696.648415 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.870 130.082 208.146 C,1.2491710205,-2.2226657059,1.0617387658 C,1.6198943449,-4.7248404497,1.0092068557 C,-0.4298577084,-3.7546423988,-0.0879695608 C,0.1456430191,-4.9538925914,0.6708390129 C,-0.233273135,-2.4895471015,0.7452149164 C,1.80796011,-3.4369989714,1.8129666998 H,2.1966008422,-4.6576848959,0.076991544 H,0.0808809005,-3.6635375588,-1.0499422713 H,-0.4212742658,-5.1057820304,1.5986846356 H,-0.7266010533,-2.6512505502,1.7110981482 H,1.2915090471,-3.5174421422,2.7785540268 H,1.7996179782,-2.093114787,0.1213268597 H,2.0184728547,-5.5749054874,1.5718636755 H,-1.4980243118,-3.8915815095,-0.2871384151 H,0.0268690876,-5.8598414406,0.0687258959 H,2.8674206791,-3.2590282936,2.024576075 N,-0.8825537683,-1.2965307574,0.1414487765 N,1.333707659,-1.0392784894,1.9039691028 C,2.0420823766,-0.0746350096,1.4768041 C,-1.6949248996,-0.6639289162,0.9148338936 H,-1.8093437265,-1.040239073,1.9326878759 H,2.5761272726,-0.1278707686,0.5168259238 C,-2.4605260752,0.5554644705,0.6304818714 C,-3.7477415609,3.0037726794,0.269117049 C,-3.0257649954,0.8706707215,-0.6118259217 C,-2.5877145595,1.45322343,1.7017523413 C,-3.2120948336,2.6799942821,1.5159226006 171 C,-3.6667092716,2.0950665284,-0.7843367327 H,-2.9699557623,0.1629328955,-1.4318183793 H,-2.1672561182,1.1931142994,2.6694197801 H,-3.2841753045,3.3810646744,2.3409514141 H,-4.1013256315,2.3393796519,-1.7482894573 H,-4.2388446026,3.9606721935,0.1220834157 C,2.2115151156,1.1861996688,2.2270606375 C,2.5771205431,3.592427225,3.5995161072 C,3.1103448157,2.1426410191,1.7476775183 C,1.4858303499,1.446408868,3.3953980366 C,1.6670419539,2.644908266,4.0759691019 C,3.2982611064,3.3401634234,2.4343177694 H,3.6641889075,1.9418702203,0.8338186972 H,0.7849239561,0.7005411402,3.7581705249 H,1.1018240839,2.8438180475,4.9813865458 H,4.0020223162,4.0761714307,2.0583246763 H,2.7192206638,4.5255796258,4.1359257805 H,2.3444899051,-3.1017620673,-3.3764977606 C,1.2932058933,-3.0003535617,-3.626223748 C,-1.4676516913,-2.7289689576,-4.2437315223 C,0.4668146414,-2.1785754338,-2.8859331061 C,0.7194533906,-3.6957908088,-4.7066203213 C,-0.6303103401,-3.5619780671,-5.00844054 C,-0.8971181253,-2.0438091266,-3.1889188986 H,1.3452367717,-4.3455362072,-5.3102170984 H,-1.0513672366,-4.108462335,-5.8465249938 H,-2.5232268817,-2.6209519667,-4.4705329045 O,-1.4909539648,-1.1885537664,-2.3248007319 O,0.7880939265,-1.4245990951,-1.8063870597 B,-0.4477119325,-0.7429859487,-1.3658401482 H,0.5884331044,3.8350130206,1.5900938527 C,0.2471046597,4.0024735786,0.5731245175 C,-0.6872154954,4.3929417611,-2.1030311512 C,0.0440894113,2.9486744486,-0.2964333569 C,-0.0297162643,5.2817836839,0.0742474557 C,-0.483653016,5.4719068731,-1.2328129815 C,-0.4149568567,3.1351147978,-1.5997459624 H,0.1086691534,6.1426713513,0.7202441854 H,-0.6893071131,6.4779904348,-1.5835089561 H,-1.0481107195,4.5317925832,-3.1162453642 O,-0.5590699678,1.9139394096,-2.2028835339 O,0.2018960201,1.6095167133,-0.0706803822 B,-0.2474066825,0.9616627937,-1.2260293929 172 IA-E,Z[1,1]DMF (Intermediate monocoordinate E-coordinated 1,1-B2cat2-E,Z-diimine 1 complex in DMF) E-coord_cydiimph2_EZ_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1419163 Zero-point correction= 0.571675 (Hartree/Particle) Thermal correction to Energy= 0.603956 Thermal correction to Enthalpy= 0.604900 Thermal correction to Gibbs Free Energy= 0.505967 Sum of electronic and ZPE= -1696.570241 Sum of electronic and thermal Energies= -1696.537961 Sum of electronic and thermal Enthalpies= -1696.537016 Sum of electronic and thermal Free Energies= -1696.635949 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.988 129.993 208.221 C,0.7658525336,-1.8647022519,1.5360039015 C,1.1418389893,-4.3705107957,1.4633270215 C,-0.8604352264,-3.3909413426,0.2934101858 C,-0.3202949485,-4.5939419874,1.0721107094 C,-0.6966388423,-2.133277006,1.1431263614 C,1.3039959513,-3.0918479449,2.2864780291 H,1.750713457,-4.2959323026,0.5525294923 H,-0.3068488926,-3.3009190168,-0.6434636012 H,-0.9208806272,-4.7455516588,1.978593887 H,-1.2351849196,-2.301616256,2.0833242372 H,0.75831001,-3.1838940385,3.2347911502 H,1.3603144316,-1.7161413284,0.631379117 H,1.5197622212,-5.2256278687,2.0326458376 H,-1.9192226244,-3.5247355052,0.0472871025 H,-0.4196692836,-5.4984666562,0.4644077869 H,2.3564049721,-2.9128232421,2.5318409048 N,-1.3026318853,-0.9202432218,0.5344806837 N,0.7680285439,-0.7281302114,2.4493982957 C,1.7046126356,0.1313044283,2.462766512 C,-2.0747079003,-0.2457527808,1.3139052178 H,-2.2060482257,-0.6209684962,2.329195354 H,1.638997679,0.8926177501,3.2478846976 C,-2.7637246447,1.0193453108,1.0352455912 C,-3.8922076605,3.5448981568,0.6808011025 C,-3.3233844416,1.3665346502,-0.2008320974 C,-2.8198775128,1.9254118661,2.1054306556 C,-3.3644046516,3.1899860042,1.9227180587 173 C,-3.8853757811,2.6296008395,-0.3698302768 H,-3.3231218365,0.6543895451,-1.0189879418 H,-2.4061141953,1.6392683517,3.0686575833 H,-3.3810542762,3.8965606441,2.745977074 H,-4.315029244,2.8992394602,-1.3292341245 H,-4.3204318248,4.531866502,0.535972019 C,2.9296952047,0.2487128154,1.6203556325 C,5.3072820311,0.5488550312,0.1735893183 C,4.1406580363,0.4827494233,2.2827681036 C,2.9156474514,0.1968028381,0.2217969259 C,4.1005797575,0.347188126,-0.4943502477 C,5.3257045402,0.6180470279,1.5654683132 H,4.149649395,0.5537010715,3.367500624 H,1.9813273932,0.0526663451,-0.3105885856 H,4.0785421768,0.3107061571,-1.5792459115 H,6.2601875458,0.7861790463,2.091572783 H,6.2285595334,0.6628181494,-0.3892582575 H,1.8382541049,-2.8355182982,-3.0182350686 C,0.7926925153,-2.6834319488,-3.266428758 C,-1.952209688,-2.2749877386,-3.8792678532 C,0.0014048739,-1.8448859942,-2.5074225339 C,0.1910782992,-3.3258615195,-4.3642395207 C,-1.1511814721,-3.1252028372,-4.663223399 C,-1.3543133851,-1.6418718074,-2.8068202196 H,0.7886234248,-3.9873696431,-4.9834355986 H,-1.5944525526,-3.6314192683,-5.5149984249 H,-3.001430923,-2.1143350334,-4.104290203 O,-1.9122892313,-0.7816357731,-1.9243887991 O,0.3536243655,-1.1328237699,-1.4076846747 B,-0.8492387692,-0.3895149723,-0.9634538187 H,0.5941484183,4.2494177451,1.78043038 C,0.2004862339,4.3872545462,0.7792151523 C,-0.8525930087,4.7167224803,-1.8584114761 C,-0.1141415618,3.3086462165,-0.0244209127 C,-0.0274399922,5.6581545087,0.2363526983 C,-0.541300726,5.818856825,-1.0519958033 C,-0.6265129325,3.468294648,-1.3112922602 H,0.1991552936,6.5358971459,0.832678801 H,-0.7068905446,6.8191325022,-1.4385581251 H,-1.2561820231,4.8309900384,-2.8584664331 O,-0.8657438644,2.2349890704,-1.853960194 O,-0.0231900323,1.9712575163,0.2553109965 B,-0.5597318678,1.3058197926,-0.8539431873 174 IA-Z,E[1,1]DMF (Intermediate monocoordinate Z-coordinated 1,1-B2cat2-Z,E-diimine 1 complex in DMF) Z-coord_cydiimph2_ZE_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1579023 Zero-point correction= 0.571120 (Hartree/Particle) Thermal correction to Energy= 0.603444 Thermal correction to Enthalpy= 0.604388 Thermal correction to Gibbs Free Energy= 0.504877 Sum of electronic and ZPE= -1696.586782 Sum of electronic and thermal Energies= -1696.554459 Sum of electronic and thermal Enthalpies= -1696.553515 Sum of electronic and thermal Free Energies= -1696.653025 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.667 130.131 209.437 C,-0.3621591731,0.391350036,1.9677351304 C,-1.7947014145,0.7206047835,4.0487233824 C,-2.8978645348,0.5823594002,1.8002365218 C,-2.9531593839,1.2236711181,3.186621333 C,-1.5520359591,0.8983830753,1.14054954 C,-0.4505033344,0.9990462837,3.3770077292 H,-1.9063808389,-0.3600783361,4.2061133872 H,-3.0101469512,-0.5012685351,1.8921367142 H,-2.8914976751,2.3161226809,3.0908744819 H,-1.4274672479,1.98454216,1.094632265 H,-0.2963073398,2.0826704813,3.2871597886 H,-0.3892357422,-0.706404421,2.0441370652 H,-1.8159700961,1.1933061775,5.0357295633 H,-3.7105386111,0.9436481519,1.1605094094 H,-3.9121824145,0.994486951,3.6611826139 H,0.3770120126,0.6030601956,3.974911077 N,-1.4789532521,0.3830171181,-0.2398440864 N,0.8619611508,0.8560371322,1.3208869326 C,1.9511623905,0.2744666175,1.6264691558 C,-1.5006379511,1.1549760077,-1.2648668303 H,-1.3504376847,0.6516705575,-2.2200087683 H,1.9872990802,-0.5783189051,2.3213725022 C,-1.668761454,2.6148320813,-1.3444567464 C,-1.8967957193,5.3749395339,-1.6966958259 C,-0.9128567937,3.2685216339,-2.3276643017 C,-2.5710287502,3.3512747783,-0.5641128064 C,-2.6841324823,4.7249840207,-0.7471086258 175 C,-1.0105792619,4.6458925424,-2.4876292461 H,-0.2413116589,2.6901988233,-2.9562399842 H,-3.2071966778,2.8522030196,0.1593512591 H,-3.3923924387,5.2883937765,-0.1486784752 H,-0.407742107,5.1469905508,-3.237711146 H,-1.9854463052,6.4485292111,-1.8298959647 C,3.2484724262,0.711730457,1.0729947529 C,5.7208735092,1.479939362,0.0289277942 C,4.4248816737,0.1251398032,1.5458017134 C,3.3151813205,1.6890856136,0.0713070835 C,4.5459889528,2.0677632203,-0.4483110467 C,5.659763252,0.5114761176,1.027772264 H,4.3679644548,-0.6400728333,2.3162394023 H,2.3935057454,2.129803727,-0.296231699 H,4.5954642918,2.8200990921,-1.2295546224 H,6.5703553073,0.0505978154,1.3977559469 H,6.6810579927,1.7771843412,-0.3813785646 H,-4.2591471046,-3.1033786475,1.5447839156 C,-4.234501953,-2.889708453,0.4809458249 C,-4.1397037836,-2.3292502772,-2.3042399202 C,-3.1133372944,-2.3312473442,-0.1026862647 C,-5.3296700241,-3.1723431203,-0.3540206727 C,-5.282971036,-2.8983905554,-1.7166089655 C,-3.0675594553,-2.0509623371,-1.4783408839 H,-6.2247681823,-3.6101287579,0.0765432842 H,-6.1419085832,-3.1244535135,-2.3406131405 H,-4.0939636604,-2.1123460826,-3.3664739714 O,-1.8621110329,-1.5245035368,-1.813830824 O,-1.9398115574,-1.9937907089,0.4892974881 B,-1.1940633399,-1.2318778095,-0.5255647518 H,3.3863195716,-3.8858252752,1.1761637637 C,3.5179366951,-3.1901513175,0.3545808343 C,3.8341361174,-1.3482670994,-1.8099642854 C,2.4591279542,-2.4534275518,-0.1425673204 C,4.7608350808,-2.9885320534,-0.2576024936 C,4.9145541732,-2.0885781561,-1.315539037 C,2.6122518888,-1.556470321,-1.1977846178 H,5.6223972598,-3.5433892855,0.0992703783 H,5.8944946879,-1.9542901004,-1.76228241 H,3.9451200295,-0.6425301779,-2.6260019605 O,1.4022824662,-0.9767735491,-1.4699546692 O,1.1492281652,-2.4506428807,0.2585791404 B,0.4920106105,-1.527707507,-0.5611255104 176 IA-Z,Z[1,1]DMF (Intermediate monocoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in DMF) Z-coord_cydiimph2_ZZ_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1469195 Zero-point correction= 0.572178 (Hartree/Particle) Thermal correction to Energy= 0.604172 Thermal correction to Enthalpy= 0.605116 Thermal correction to Gibbs Free Energy= 0.507406 Sum of electronic and ZPE= -1696.574742 Sum of electronic and thermal Energies= -1696.542748 Sum of electronic and thermal Enthalpies= -1696.541803 Sum of electronic and thermal Free Energies= -1696.639513 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.124 129.684 205.647 C,0.7507412676,-0.9544908556,0.7008025908 C,1.7900402077,-3.2713721595,0.7001451448 C,-0.4379090104,-2.9155217553,-0.4104823299 C,0.433430375,-3.897904214,0.3742834426 C,-0.6000590819,-1.6217064625,0.3965599302 C,1.6180087166,-1.9628688778,1.4712339356 H,2.3327553742,-3.0732678906,-0.2338365981 H,0.0313272433,-2.6980977486,-1.3725078565 H,-0.0717152808,-4.1755515812,1.308688077 H,-1.0441214283,-1.8911237409,1.3568147868 H,1.1216107324,-2.1591444063,2.4309305373 H,1.227426382,-0.6946750214,-0.2549390903 H,2.401386691,-3.9649974756,1.2860165132 H,-1.4298106713,-3.3369520322,-0.6068449036 H,0.5651333443,-4.8161559224,-0.2063741173 H,2.5884267671,-1.5123894757,1.6989281736 N,-1.5142913902,-0.6802425708,-0.281948738 N,0.4792907525,0.2180457686,1.521882277 C,1.3291643347,1.1246977045,1.8062579245 C,-2.6798225469,-0.4063638953,0.1780652142 H,-3.2890379335,0.2261311736,-0.467970527 H,0.9474124853,1.9036064024,2.4756042454 C,-3.3103280106,-0.8359898397,1.4408993808 C,-4.657963706,-1.5559055003,3.7730750182 C,-2.6693319341,-0.7248436426,2.6820498582 C,-4.6397242646,-1.2706767576,1.3792713792 C,-5.3033317858,-1.650161126,2.5411472327 177 C,-3.3486964848,-1.0815896159,3.8423754057 H,-1.6553160761,-0.3360330439,2.7279077727 H,-5.1443142667,-1.3190455539,0.4183602826 H,-6.3271601738,-2.0054044047,2.4863641332 H,-2.8549900259,-0.9855611002,4.8039906335 H,-5.1802832924,-1.8390717461,4.6815008464 C,2.7445141545,1.3770439895,1.4336865065 C,5.3867452816,2.1378756148,0.8609354921 C,3.3488463157,2.4523330983,2.1022231455 C,3.4912955432,0.6855330683,0.4658901816 C,4.7975971245,1.0708225761,0.182413146 C,4.6598419402,2.8268949029,1.8285777454 H,2.7732300458,3.0050398962,2.8406833823 H,3.0696462351,-0.1473297096,-0.0809039825 H,5.3599230433,0.5317596482,-0.5735046187 H,5.1073278243,3.6606822583,2.3602464123 H,6.407957957,2.4284085787,0.6348024171 H,0.0955097032,-2.8042021378,-4.2977756971 C,-0.8478757298,-2.2677291968,-4.2833984175 C,-3.3055407335,-0.8393755445,-4.2314169843 C,-1.0622620382,-1.2366319997,-3.3889438947 C,-1.891114907,-2.5856642891,-5.1703663235 C,-3.0927618174,-1.8860421071,-5.1456064147 C,-2.2781979055,-0.5342048534,-3.3596341667 H,-1.7522734226,-3.3916864773,-5.8839998581 H,-3.8836385189,-2.1506809579,-5.8403873117 H,-4.2398858767,-0.2881657249,-4.2050634858 O,-2.2410588087,0.4353781997,-2.4092879709 O,-0.2057324576,-0.737522858,-2.4626178161 B,-1.013359067,0.166134191,-1.6301929704 H,3.4392480549,3.4731977721,-1.6030127623 C,2.5892579396,3.8260825983,-1.0288672103 C,0.342409894,4.712485457,0.5024359253 C,1.4231932528,3.0899331374,-0.942827736 C,2.6196559543,5.031083265,-0.3172840103 C,1.5237567854,5.4613612289,0.435451978 C,0.3220564543,3.5265593459,-0.2084463904 H,3.5182211088,5.639098577,-0.3457865074 H,1.5856169529,6.3987917754,0.9784622255 H,-0.5154279291,5.0417031394,1.0784163478 O,-0.6859941767,2.6070438857,-0.3239344037 O,1.1294085172,1.8774518042,-1.5051333864 B,-0.1780839938,1.5711651953,-1.1140831514 178 IA-E,E[1,2]DMF (Intermediate monocoordinate 1,2-B2cat2-E,E-diimine 1 complex in DMF) E-coord_cydiimph2_EE_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1561642 Zero-point correction= 0.571514 (Hartree/Particle) Thermal correction to Energy= 0.603474 Thermal correction to Enthalpy= 0.604418 Thermal correction to Gibbs Free Energy= 0.507024 Sum of electronic and ZPE= -1696.584650 Sum of electronic and thermal Energies= -1696.552691 Sum of electronic and thermal Enthalpies= -1696.551747 Sum of electronic and thermal Free Energies= -1696.649140 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.685 130.169 204.983 C,0.026832825,-2.0310333089,-1.1148316986 C,1.6654189578,-3.7681327842,-1.9699319461 C,2.4133002833,-1.3827915366,-1.6852597111 C,2.5721589753,-2.6615425028,-2.5111517315 C,0.9495638772,-0.9502134237,-1.698969953 C,0.2041489059,-3.3195132689,-1.9313663891 H,1.9885468143,-4.0330157439,-0.9545633359 H,2.7383509664,-1.5882749761,-0.6602781498 H,2.3138177958,-2.4546085275,-3.5576727692 H,0.6507546623,-0.8245266481,-2.7458998053 H,-0.1601449609,-3.1310235735,-2.9498037069 H,0.3056049036,-2.2364939855,-0.0686543356 H,1.7575203026,-4.6710638971,-2.5815431175 H,3.0403609925,-0.5750589467,-2.0771489962 H,3.6181839732,-2.981586747,-2.4935043744 H,-0.4328301709,-4.0963294685,-1.4957899429 N,-1.3474087914,-1.5605961191,-1.2084203366 N,0.7279195234,0.3571814871,-1.0337708335 C,-0.0813099554,1.1512100425,-1.6471472463 H,-0.5514210926,0.7615894762,-2.5511700426 C,-2.1801472483,-2.0269433955,-0.36954436 H,-1.8879427833,-2.7594042524,0.3970092855 B,1.3725935534,0.6197254671,0.4494197736 B,1.6746283517,-0.6884256679,1.4824594692 O,2.9566478711,-1.0672202018,1.8076125281 O,0.3984995844,1.4257758537,1.1987363966 C,3.8109225441,0.7875030429,0.4605383548 179 C,6.3824392963,-0.3139150989,0.7968356152 C,3.9959832851,-0.405408834,1.1952674758 C,4.9394473922,1.4034983882,-0.0869448569 C,6.2127489818,0.8665761097,0.0781180482 C,5.2696985014,-0.9411388003,1.3507748374 H,4.785645413,2.3197911455,-0.6486536097 H,7.0677136957,1.371144179,-0.3605544809 H,5.3652705037,-1.8594362902,1.9220597756 H,7.3686945002,-0.7455159473,0.930199195 O,2.610101292,1.3759649721,0.2598784817 C,-0.6595688959,0.7491616318,1.7031627464 C,-2.873217415,-0.5479457765,2.846505212 C,-0.5296786039,-0.5431025443,2.2594053323 C,-1.9173782407,1.3564539099,1.7133012556 C,-3.0165198284,0.7188249535,2.2855695528 C,-1.628562615,-1.1754625787,2.8293333353 H,-2.0020197764,2.3491131054,1.2792277333 H,-3.9845284307,1.2104472351,2.2835525056 H,-1.4860423912,-2.1614252609,3.2617047373 H,-3.7248193917,-1.0526529402,3.2910710577 O,0.6925533937,-1.1685032038,2.3238479379 C,-0.4686817991,2.5242058349,-1.314054869 C,-1.3619865602,5.1184982375,-0.8221796401 C,0.3795903337,3.4491282636,-0.6899003769 C,-1.7472418375,2.9221102629,-1.7282042511 C,-2.2027488441,4.2085956998,-1.4600578124 C,-0.0686688504,4.7420464043,-0.4544630765 H,1.3831351814,3.1544101459,-0.4049180576 H,-2.3865191803,2.2133645484,-2.2481368439 H,-3.2022480401,4.5038156856,-1.7616371444 H,0.5910255889,5.4614032097,0.0197987202 H,-1.7073817813,6.1286920449,-0.62504703 C,-3.5962343187,-1.6124075614,-0.356745331 C,-6.2612161872,-0.7936635819,-0.2261783229 C,-4.5094704682,-2.3135785976,0.4348304966 C,-4.0238292609,-0.493766537,-1.0807790913 C,-5.3506624559,-0.0860756642,-1.0139994488 C,-5.8406138894,-1.9092617767,0.4956640199 H,-4.1685769488,-3.1714718701,1.0094595235 H,-3.3001187109,0.0543933632,-1.6768017497 H,-5.6774543275,0.7875193056,-1.5696527217 H,-6.5468904658,-2.4583751555,1.1103500493 H,-7.2965275046,-0.4714060106,-0.1723709559 180 IA-E,Z[1,2]DMF (Intermediate monocoordinate E-coordinated 1,2-B2cat2-E,Z-diimine 1 complex in DMF) E-coord_cydiimph2_EZ_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1464269 Zero-point correction= 0.572432 (Hartree/Particle) Thermal correction to Energy= 0.604117 Thermal correction to Enthalpy= 0.605061 Thermal correction to Gibbs Free Energy= 0.509305 Sum of electronic and ZPE= -1696.573995 Sum of electronic and thermal Energies= -1696.542310 Sum of electronic and thermal Enthalpies= -1696.541366 Sum of electronic and thermal Free Energies= -1696.637122 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.089 129.785 201.536 C,0.8324988004,-1.0918133394,1.7101354087 C,0.186308711,-3.384140265,2.5927066112 C,-1.6009180411,-1.8049372629,1.7966007728 C,-1.2572097804,-2.9187929179,2.7872354083 C,-0.6198554683,-0.6453528813,1.9574137723 C,1.1571595748,-2.2107614541,2.7157968469 H,0.2905381596,-3.8396354362,1.5984884903 H,-1.5357256983,-2.2130525471,0.7829293223 H,-1.3858032722,-2.5494004906,3.8127841937 H,-0.6667820482,-0.3037927956,2.9971857779 H,1.0934543058,-1.7778659364,3.7224342962 H,0.9092498824,-1.473738179,0.6827453009 H,0.4428906868,-4.1538095784,3.3272876378 H,-2.6242860631,-1.4437927884,1.9421303826 H,-1.9519837588,-3.7534464004,2.6543408985 H,2.19203391,-2.5376134767,2.5764956624 N,1.7060123921,0.0442577688,1.9385108566 N,-0.982544364,0.5176802905,1.1111902442 C,-0.8694766192,1.6659864917,1.6847690722 H,-0.4595946147,1.6669459866,2.6952785312 C,2.8951843004,0.1145647562,1.4866509434 H,3.4330332936,1.0278997255,1.7627282935 B,-1.3572234638,0.2673490702,-0.4642661992 B,-0.627931046,-1.0120587056,-1.299340212 O,-1.3617797237,-2.0828177904,-1.7561129116 O,-0.9065245976,1.4485913959,-1.2145268859 C,-3.3910716378,-1.0275572225,-0.8798414289 181 C,-4.7517024788,-3.4135783255,-1.5110108416 C,-2.7027391033,-2.123333069,-1.4486619092 C,-4.7622441496,-1.1636763029,-0.6460744697 C,-5.4410992905,-2.3375884235,-0.9579716691 C,-3.3855529991,-3.2965043115,-1.7516346194 H,-5.2798492462,-0.3155629027,-0.2084015268 H,-6.5065208917,-2.4080235679,-0.7632353538 H,-2.8171566104,-4.1129561923,-2.186511197 H,-5.2670939546,-4.3361467191,-1.7560438407 O,-2.8113619701,0.1471253456,-0.5462534715 C,0.422682847,1.5224100958,-1.4562296187 C,3.1589234503,1.7617824324,-2.0347724285 C,1.1952127132,0.3804153782,-1.7707052808 C,1.050356708,2.7689442792,-1.4321128276 C,2.4081608855,2.8915421356,-1.7205417783 C,2.5464298793,0.5098463167,-2.0653681388 H,0.4410357739,3.6362028373,-1.1923387054 H,2.8752347334,3.8711180352,-1.6976719267 H,3.1087549709,-0.3874659916,-2.3091945787 H,4.2177133709,1.8458588388,-2.2582038318 O,0.6137551367,-0.8607899881,-1.8814628072 C,-1.2315730745,2.991139463,1.1759682929 C,-1.8228799051,5.5878888214,0.3594487235 C,-2.3275357268,3.225670375,0.3351884235 C,-0.4627612356,4.067521339,1.6375130642 C,-0.7425133668,5.3611635566,1.2103437448 C,-2.6219343316,4.5233817437,-0.0624191176 H,-2.9432645931,2.3950124836,0.0078129445 H,0.3653648151,3.8803344261,2.3158289947 H,-0.1299670226,6.1894394048,1.5507568994 H,-3.4756717008,4.7083413115,-0.706222303 H,-2.0542047978,6.5981271169,0.0360278558 C,3.7257025927,-0.7657021595,0.6232953706 C,5.450740177,-2.1261889958,-1.1347274332 C,4.9410854446,-0.1966081579,0.2104394916 C,3.4029759546,-2.0500866237,0.1545600863 C,4.2598910911,-2.7171841303,-0.7171497733 C,5.7948186329,-0.861366804,-0.6611138132 H,5.2046689139,0.7957328423,0.5673578029 H,2.4970129369,-2.5553925455,0.4594564648 H,3.9921825713,-3.7080082408,-1.0702426575 H,6.7240977914,-0.3939492623,-0.9710496876 H,6.1103512389,-2.6524968823,-1.8176326391 182 IA-Z,E[1,2]DMF (Intermediate monocoordinate Z-coordinated 1,2-B2cat2-Z,E-diimine 1 complex in DMF) Z-coord_cydiimph2_ZE_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1566691 Zero-point correction= 0.571676 (Hartree/Particle) Thermal correction to Energy= 0.603690 Thermal correction to Enthalpy= 0.604634 Thermal correction to Gibbs Free Energy= 0.506849 Sum of electronic and ZPE= -1696.584993 Sum of electronic and thermal Energies= -1696.552979 Sum of electronic and thermal Enthalpies= -1696.552035 Sum of electronic and thermal Free Energies= -1696.649820 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.821 130.109 205.805 C,0.2061064972,0.008270096,1.8153146362 C,-1.2927054462,0.1352180793,3.874077928 C,-2.2107897156,0.868477417,1.6636204735 C,-2.2035685529,1.1386150593,3.1677125539 C,-0.7921214792,0.943114221,1.1032576214 C,0.1322876884,0.2314684409,3.3334207036 H,-1.6813582209,-0.8796388139,3.7153389201 H,-2.6310484184,-0.1278900656,1.5004576778 H,-1.8463477073,2.1583782361,3.3615060511 H,-0.4104546076,1.9531165988,1.2615896299 H,0.5386392198,1.2291767656,3.5440869184 H,-0.0344009417,-1.0439461514,1.5839324074 H,-1.2873216348,0.3124211667,4.9540148308 H,-2.8452624181,1.5843353338,1.1291148631 H,-3.2250833086,1.073447991,3.5539110285 H,0.7921565037,-0.4954332311,3.8179012109 N,1.5397463071,0.3766304275,1.3710533699 N,-0.7509569746,0.6382135246,-0.3398157 C,-0.0754900624,1.3431951557,-1.1716728325 H,-0.0047268757,0.9248203259,-2.1764882208 C,2.3498323424,-0.5374349506,1.0189951201 H,2.0690950365,-1.6012208426,1.0053040534 B,-1.5368515437,-0.6637848425,-0.9837293167 B,-2.03172669,-1.9699461423,-0.0360518076 O,-3.3565631749,-2.165366593,0.2777135662 O,-0.6113952275,-1.2243646746,-1.9775357391 C,-3.9219006469,-0.2234654077,-1.0966680748 183 C,-6.5161997813,-0.3567828632,-0.0044933907 C,-4.2546684035,-1.208491771,-0.1383110602 C,-4.9191234786,0.6736742324,-1.4885843087 C,-6.203383477,0.6108893999,-0.9555762004 C,-5.5364544809,-1.2611051032,0.397301937 H,-4.6537738654,1.4241776317,-2.2267618422 H,-6.9543201085,1.323031756,-1.2826926189 H,-5.7473727122,-2.0329315164,1.1311866039 H,-7.5121494042,-0.4138829262,0.4216689104 O,-2.7022634053,-0.1083090694,-1.6671438806 C,0.3057812904,-2.0992095315,-1.4987607862 C,2.2381080483,-3.9575512566,-0.6443360284 C,0.0242383645,-3.0058532545,-0.449492544 C,1.5717095701,-2.1410154839,-2.0870538552 C,2.528686486,-3.0642141714,-1.6730183494 C,0.9850274315,-3.9217933873,-0.0362651785 H,1.7791287933,-1.4388842655,-2.889247916 H,3.5032544176,-3.0767124211,-2.1510568836 H,0.7246130724,-4.6086976134,0.7631653124 H,2.9778198335,-4.6800657738,-0.3149923192 O,-1.213095892,-3.0627682517,0.1454067554 C,0.629956295,2.6186882173,-0.9554580242 C,2.0475694019,5.0051311083,-0.7052346642 C,0.0350571326,3.7231607399,-0.3330207001 C,1.9198805079,2.7284296914,-1.4872755265 C,2.634818637,3.9132232287,-1.3417208078 C,0.7449629892,4.9130732744,-0.2149626886 H,-0.9865051462,3.6592092078,0.0305578548 H,2.3642763211,1.8767268588,-1.9958158951 H,3.6441330733,3.9857744169,-1.7341792339 H,0.2792498618,5.7711576946,0.2583906699 H,2.5993942985,5.9341866665,-0.6031449238 C,3.7381657523,-0.2218827684,0.6200068992 C,6.366871682,0.3362349152,-0.1473811808 C,4.6279595604,-1.2628065565,0.3403837526 C,4.1797344663,1.1046518567,0.5270103437 C,5.4851542819,1.3808075091,0.1399947949 C,5.9388911856,-0.9850916585,-0.0410721869 H,4.2869196774,-2.2909783312,0.4242031412 H,3.4875473081,1.9073253482,0.7608034575 H,5.8198307576,2.4109922884,0.0638459892 H,6.6241637066,-1.799091273,-0.2556320706 H,7.3867140027,0.5544140815,-0.4490822301 184 IA-Z,Z[1,2]DMF (Intermediate monocoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in DMF) Z-coord_cydiimph2_ZZ_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.145746 Zero-point correction= 0.572509 (Hartree/Particle) Thermal correction to Energy= 0.604250 Thermal correction to Enthalpy= 0.605194 Thermal correction to Gibbs Free Energy= 0.508946 Sum of electronic and ZPE= -1696.573237 Sum of electronic and thermal Energies= -1696.541496 Sum of electronic and thermal Enthalpies= -1696.540552 Sum of electronic and thermal Free Energies= -1696.636800 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.173 129.694 202.571 C,-1.0853016496,-0.8044116699,0.1726338613 C,-2.7316267883,-0.9304514789,2.0999297667 C,-0.3173298349,-0.3989525598,2.558823195 C,-1.5796565811,-1.0748058865,3.0953913668 C,0.0500586668,-0.9871414492,1.1990825013 C,-2.3437729721,-1.4889068637,0.7313915103 H,-2.9921008713,0.1319190644,1.9981187311 H,-0.51189512,0.6744158355,2.4558763047 H,-1.3787616883,-2.1400798588,3.2682226129 H,0.1941848988,-2.0637062099,1.304414972 H,-2.1285443797,-2.5621547919,0.8124532797 H,-1.2661972847,0.2718403397,0.0433557548 H,-3.6235388988,-1.445962212,2.4694038341 H,0.5239546186,-0.5150523388,3.2504950899 H,-1.8486869534,-0.6356744196,4.0606817634 H,-3.1636799853,-1.3822963985,0.014530703 N,-0.679847885,-1.4429768884,-1.0660852112 N,1.2879278438,-0.4015900041,0.6551570857 C,2.2036759357,-1.1310546342,0.1318759178 H,3.0084438032,-0.5820586563,-0.3571311794 C,-1.199572937,-1.1744965304,-2.1977284521 H,-0.7949570309,-1.7587263431,-3.0314753009 B,1.5228601434,1.2246612745,0.6655198671 B,0.2268332526,2.2862257449,0.4661474114 O,-0.2006658381,3.1016294688,1.4871237017 O,2.4066581355,1.4993291037,-0.4801265256 C,1.6273089754,2.2471833709,2.879584714 185 C,0.5160582791,3.7204247488,5.0121359346 C,0.4474244314,3.0058970376,2.6984579383 C,2.2226223132,2.2557937694,4.1445006717 C,1.6822595439,2.9832899079,5.2003689519 C,-0.0917975628,3.7249696574,3.7597910571 H,3.1272263428,1.6692619666,4.2723999733 H,2.1728670618,2.967099161,6.1684016692 H,-0.9984644978,4.2927886012,3.574575808 H,0.0809586146,4.2894284257,5.8268079267 O,2.2185033078,1.5092598745,1.915183227 C,1.7822324133,1.5444752378,-1.6842428289 C,0.5901245121,1.6566489964,-4.2265684342 C,0.485695123,2.0864601004,-1.8498252551 C,2.447487451,1.0562093155,-2.8099370894 C,1.8618668893,1.1118364019,-4.073132445 C,-0.0894993415,2.1465636673,-3.1130123408 H,3.442112937,0.6425648366,-2.6704768673 H,2.4020475335,0.7269297644,-4.9322461501 H,-1.0854031513,2.5721195513,-3.2023620243 H,0.1213794516,1.702180768,-5.2043534121 O,-0.2059263048,2.6353000199,-0.7953905773 C,2.3084384777,-2.6026774528,0.1031635201 C,2.6443504513,-5.3636764671,-0.0551446578 C,2.2310245214,-3.3832608253,1.2618671951 C,2.5851809524,-3.2051138828,-1.1289193185 C,2.7330411722,-4.5857222266,-1.2087520209 C,2.4045616161,-4.7611554273,1.1788738161 H,2.0570815501,-2.9097250215,2.2241681793 H,2.6684618471,-2.5880108312,-2.0196742041 H,2.9286039945,-5.0530419658,-2.1683443853 H,2.3535259994,-5.3640965046,2.0795867894 H,2.7726052764,-6.4397487015,-0.1161497194 C,-2.2307648895,-0.208147468,-2.6594329871 C,-4.0044910203,1.6266804871,-3.8455556433 C,-2.3796885265,-0.1366381994,-4.0538665756 C,-3.0128967564,0.6474438092,-1.8655524301 C,-3.8863486757,1.5554248753,-2.4589989252 C,-3.2509111607,0.7695909148,-4.6456168039 H,-1.7824956236,-0.7937547487,-4.6807428929 H,-2.9674932018,0.6215203467,-0.7853801745 H,-4.480400493,2.2099934138,-1.8291495308 H,-3.3404759783,0.8083718937,-5.726614799 H,-4.6864544852,2.3395371739,-4.2985074303 186 IA-E,E[1,1]benzene (Intermediate monocoordinate 1,1-B2cat2-E,E-diimine 1 complex in benzene) E-coord_cydiimph2_EE_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1512803 Zero-point correction= 0.572327 (Hartree/Particle) Thermal correction to Energy= 0.604352 Thermal correction to Enthalpy= 0.605296 Thermal correction to Gibbs Free Energy= 0.508483 Sum of electronic and ZPE= -1696.578953 Sum of electronic and thermal Energies= -1696.546929 Sum of electronic and thermal Enthalpies= -1696.545985 Sum of electronic and thermal Free Energies= -1696.642798 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.236 129.867 203.760 C,1.2418853962,-2.2136502716,1.0590259292 C,1.6093419376,-4.7168347712,0.9884651002 C,-0.4497283771,-3.7409132878,-0.0861602906 C,0.131660526,-4.9433996912,0.6628737641 C,-0.2417143298,-2.4756771649,0.7446851305 C,1.8048466141,-3.4336138085,1.7978796941 H,2.1757604526,-4.6449188693,0.0505602922 H,0.0478308676,-3.6485373129,-1.0542955308 H,-0.4257825634,-5.1026572259,1.5957606358 H,-0.7306023073,-2.6308012732,1.7153215964 H,1.2985362885,-3.5164999495,2.7685928922 H,1.7853725016,-2.0751797538,0.1157198307 H,2.0140822059,-5.5706749773,1.5407781232 H,-1.5195171706,-3.8752839143,-0.2777536048 H,0.0061499561,-5.8461074044,0.0577766265 H,2.8652381284,-3.2569237285,2.0045428235 N,-0.8836175383,-1.2828596401,0.1380115702 N,1.32509215,-1.0402241242,1.9128848202 C,2.0275583337,-0.0684475221,1.494474676 C,-1.681059886,-0.6319231101,0.9090188539 H,-1.7802156335,-0.989118848,1.9361552306 H,2.5505368762,-0.1061201368,0.5271866036 C,-2.4500205711,0.5809966343,0.60772447 C,-3.7503080375,3.0122346462,0.191226779 C,-3.0305922005,0.8573920206,-0.6363304378 C,-2.5665376096,1.5095943208,1.6528119996 C,-3.197531264,2.7274026315,1.4393629111 187 C,-3.6790210118,2.0732669938,-0.8346965188 H,-2.9720481356,0.1296448244,-1.4386838383 H,-2.1229540375,1.2855657141,2.6191927924 H,-3.255097257,3.455324813,2.2416133644 H,-4.1198316003,2.2892930695,-1.8022197479 H,-4.2412495594,3.9649455583,0.0207854475 C,2.2008707941,1.1796746332,2.2636119729 C,2.5708314423,3.5562024781,3.6822692076 C,3.0671813064,2.1621826373,1.7800013247 C,1.5111507225,1.3975532023,3.4612482041 C,1.6935398278,2.5816500428,4.1642548007 C,3.2578784164,3.3450466309,2.4896805619 H,3.5905375093,1.9967680806,0.8417039787 H,0.8418834445,0.6238003887,3.8244604022 H,1.1574654738,2.748007206,5.0935624777 H,3.9347238493,4.1026998373,2.1081202893 H,2.7153667459,4.4780339845,4.2370987041 H,2.3452013784,-3.1261013309,-3.3600378306 C,1.2947907239,-3.0265690015,-3.6124958413 C,-1.4621508891,-2.7479794028,-4.2385664628 C,0.4713516839,-2.1912024746,-2.8859106076 C,0.719493427,-3.7318706782,-4.6838236139 C,-0.6285529137,-3.5951175139,-4.9889603826 C,-0.8896390252,-2.0523942883,-3.1930340321 H,1.3422566517,-4.3917324757,-5.2790834553 H,-1.0500568521,-4.1497242535,-5.8211559237 H,-2.5161613064,-2.6347843634,-4.4677586359 O,-1.4800615435,-1.1827618722,-2.3380992372 O,0.7928779434,-1.4270725129,-1.8103409472 B,-0.4375562798,-0.734684107,-1.3902747469 H,0.6162971732,3.8305811067,1.5777693424 C,0.2654137877,4.0029079328,0.565429061 C,-0.6850533408,4.3991105715,-2.10233628 C,0.0592665182,2.9515455854,-0.305369135 C,-0.0168778194,5.2821820222,0.0719992322 C,-0.4782239438,5.4754175546,-1.231229754 C,-0.4091370093,3.1403364836,-1.6046173973 H,0.1253691502,6.1417789731,0.7187746309 H,-0.6853434031,6.4823974365,-1.5783198758 H,-1.0504857338,4.5372242471,-3.1136222449 O,-0.5587201962,1.9222774063,-2.209540777 O,0.221683756,1.6112184615,-0.0854750661 B,-0.233874604,0.9681028707,-1.2422239209 188 IA-E,Z[1,1]benzene (Intermediate monocoordinate E-coordinated 1,1-B2cat2-E,Z-diimine 1 complex in benzene) E-coord_cydiimph2_EZ_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1398021 Zero-point correction= 0.572332 (Hartree/Particle) Thermal correction to Energy= 0.604714 Thermal correction to Enthalpy= 0.605658 Thermal correction to Gibbs Free Energy= 0.504414 Sum of electronic and ZPE= -1696.567470 Sum of electronic and thermal Energies= -1696.535088 Sum of electronic and thermal Enthalpies= -1696.534144 Sum of electronic and thermal Free Energies= -1696.635389 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.464 129.827 213.088 C,0.740533225,-1.8409345647,1.5140676628 C,1.1872053749,-4.3346737048,1.4207618883 C,-0.8559959867,-3.4069127267,0.2772958484 C,-0.2714212423,-4.5988593242,1.0408926696 C,-0.717246441,-2.149758308,1.1323075657 C,1.3208686458,-3.0568290979,2.2508585547 H,1.7843272845,-4.2365319541,0.5047860381 H,-0.3200878096,-3.2934805419,-0.66678656 H,-0.8578475886,-4.7796729443,1.9518418794 H,-1.2363463022,-2.3372122162,2.0809678804 H,0.7900561602,-3.1676615196,3.2057445922 H,1.3199803998,-1.6694198795,0.6042358416 H,1.5961649295,-5.1827914163,1.9789648304 H,-1.9126298647,-3.5698540954,0.0399535781 H,-0.3496149613,-5.5006979345,0.4265665378 H,2.3698075519,-2.8495302658,2.487127135 N,-1.3637840989,-0.9534257316,0.5378131297 N,0.7085439094,-0.7118939152,2.434111812 C,1.6110929638,0.1819513859,2.4484553943 C,-2.1372362267,-0.2963217013,1.3282037787 H,-2.232881864,-0.6701973991,2.3485447862 H,1.5110755174,0.9362062219,3.2373930743 C,-2.8797318588,0.9388508192,1.0585635135 C,-4.191829421,3.3782270295,0.7437968935 C,-3.4396724789,1.2761754116,-0.1810828353 C,-3.019179395,1.8138394994,2.1463566052 C,-3.6569204317,3.0356074982,1.9850435476 189 C,-4.0931147866,2.495937171,-0.3289326064 H,-3.3745535019,0.5869984209,-1.0159121174 H,-2.5983855672,1.5381232744,3.1094996256 H,-3.740391908,3.7186248574,2.8236145723 H,-4.5230525895,2.7563799356,-1.2901897269 H,-4.6948221561,4.3314045045,0.6159628195 C,2.8348067918,0.3563384087,1.6143081498 C,5.213284535,0.766004293,0.1964506044 C,4.0194179977,0.6790260671,2.2865142971 C,2.8471163176,0.2703421202,0.2174158619 C,4.0323555648,0.4755773041,-0.4827257833 C,5.2053877505,0.8690817489,1.585355684 H,4.0077351941,0.7749550943,3.3694618397 H,1.9333937485,0.0623463472,-0.3287632478 H,4.028004923,0.4138217065,-1.5663776192 H,6.1189643634,1.1068790537,2.1209726396 H,6.1342838925,0.9233986053,-0.356021786 H,1.7847678588,-2.7849854083,-3.0337232925 C,0.7359310048,-2.6514030439,-3.2771719167 C,-2.0168244542,-2.2846178008,-3.8741173312 C,-0.0630688291,-1.8228873109,-2.5168137604 C,0.1375217714,-3.3048774918,-4.3684306889 C,-1.2087124283,-3.1248720186,-4.6589507978 C,-1.421735549,-1.6399767714,-2.8084425368 H,0.7402884429,-3.9586597391,-4.9903163561 H,-1.6488745153,-3.6397293135,-5.5068766504 H,-3.069063366,-2.1380728196,-4.0921485919 O,-1.9870643638,-0.7863402224,-1.9214017775 O,0.2831697337,-1.1065101907,-1.4150546706 B,-0.9305101702,-0.3897132337,-0.9654785663 H,1.0011117381,4.0871356455,1.7383835395 C,0.5882821889,4.2694837838,0.7525564889 C,-0.4937801922,4.7095668267,-1.8538044708 C,0.0790184819,3.2388547842,-0.0119296254 C,0.5445865312,5.5488847386,0.1866153939 C,0.0150058559,5.7637622575,-1.0863973127 C,-0.4464606443,3.4519637373,-1.2849931689 H,0.9332713326,6.3902992439,0.7506005867 H,-0.0010869182,6.769360787,-1.4934023418 H,-0.9035980867,4.8629777474,-2.8456145965 O,-0.8672046788,2.2571716476,-1.8015533875 O,-0.0110518446,1.9059652441,0.287816223 B,-0.6215794601,1.2977814434,-0.8167692503 190 IA-Z,E[1,1]benzene (Intermediate monocoordinate Z-coordinated 1,1-B2cat2-Z,E-diimine 1 complex in benzene) Z-coord_cydiimph2_ZE_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1533605 Zero-point correction= 0.572028 (Hartree/Particle) Thermal correction to Energy= 0.604234 Thermal correction to Enthalpy= 0.605179 Thermal correction to Gibbs Free Energy= 0.506674 Sum of electronic and ZPE= -1696.581333 Sum of electronic and thermal Energies= -1696.549126 Sum of electronic and thermal Enthalpies= -1696.548182 Sum of electronic and thermal Free Energies= -1696.646687 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.163 129.934 207.321 C,-0.3902313891,0.4286517389,1.9788210095 C,-1.842218909,0.7988819858,4.0400774719 C,-2.9286170197,0.6213917848,1.7855094818 C,-2.9915894155,1.290220693,3.1587516561 C,-1.5757094882,0.9136156694,1.1296497833 C,-0.4913998971,1.0629082721,3.3754037055 H,-1.9590889914,-0.2784508897,4.2142630424 H,-3.0506545351,-0.458933193,1.8952186557 H,-2.9246874843,2.381139569,3.0460499867 H,-1.4431044203,1.9971660079,1.0483177329 H,-0.3310248469,2.1438199091,3.2667562966 H,-0.4140739954,-0.6682433669,2.072822802 H,-1.8723077729,1.2869992578,5.0192750712 H,-3.7359531568,0.9715493664,1.132260608 H,-3.9554124664,1.0755621527,3.6300088733 H,0.3301966568,0.6789847345,3.9891654719 N,-1.4891494382,0.3467957782,-0.2271587107 N,0.8286409154,0.8961631866,1.3303012674 C,1.9215496732,0.3067992323,1.6006320308 C,-1.4488401633,1.0748843774,-1.2805899536 H,-1.2930064863,0.5220451948,-2.2076512239 H,1.9691062656,-0.5666063962,2.2703334946 C,-1.5566350483,2.5376365771,-1.4179169112 C,-1.6741789185,5.2909975537,-1.8570129152 C,-0.7157845078,3.1400415675,-2.361985899 C,-2.4843606613,3.3220837297,-0.7213089885 C,-2.5426291052,4.6924618528,-0.9463662264 191 C,-0.7601374234,4.5140986188,-2.5649899657 H,-0.0189827861,2.524351556,-2.9239471891 H,-3.1794142496,2.8582782691,-0.0288230531 H,-3.2707286943,5.2936913977,-0.4122402837 H,-0.0920780701,4.9759607294,-3.284165065 H,-1.7197593145,6.3622216436,-2.024551795 C,3.206014139,0.7584136067,1.0302380384 C,5.6449572136,1.5661368933,-0.0548702062 C,4.3946025819,0.1596353671,1.449843423 C,3.2421844006,1.7667553727,0.0589988541 C,4.4567798474,2.1651416985,-0.4805735113 C,5.6130400343,0.5653197593,0.9110779638 H,4.3611974164,-0.6353572575,2.1904813347 H,2.3063007884,2.2130000601,-0.26248154 H,4.4840274629,2.9440456036,-1.2364084935 H,6.533454879,0.0915465291,1.2376010322 H,6.5931367922,1.8798645273,-0.480511133 H,-4.260294852,-3.1062298504,1.7079837521 C,-4.252847853,-2.9228025261,0.638594012 C,-4.1934428699,-2.4506328711,-2.1620305893 C,-3.1432210351,-2.3762736585,0.0246614214 C,-5.3544564309,-3.2382311298,-0.1735438996 C,-5.3249093496,-3.0074019032,-1.5438277545 C,-3.1146962374,-2.1398725718,-1.3580907828 H,-6.2408215457,-3.6700945615,0.2799345156 H,-6.1886536445,-3.2607193199,-2.1501370018 H,-4.1576384706,-2.2692687176,-3.2308362826 O,-1.9160389024,-1.6149141418,-1.7234902114 O,-1.9653448467,-2.0075637904,0.5934761165 B,-1.2299034984,-1.2988644539,-0.457417955 H,3.416851261,-3.8589500024,1.2062539252 C,3.5299479305,-3.1561767554,0.3882970913 C,3.7868685185,-1.304277929,-1.7726069113 C,2.4501205912,-2.445763481,-0.1005913865 C,4.7632416055,-2.9220774182,-0.2297014302 C,4.8878197226,-2.0155930133,-1.2844632838 C,2.5739826109,-1.5451306198,-1.1565448915 H,5.6404951935,-3.4567095054,0.1195901584 H,5.8620505949,-1.8524030462,-1.7336150744 H,3.8748712615,-0.591156959,-2.584185441 O,1.3485229043,-0.9960004756,-1.4196144816 O,1.1450936034,-2.4732506294,0.3121921089 B,0.4586713268,-1.5734223899,-0.5068787477 192 IA-Z,Z[1,1]benzene (Intermediate monocoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in benzene) Z-coord_cydiimph2_ZZ_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1443686 Zero-point correction= 0.572632 (Hartree/Particle) Thermal correction to Energy= 0.604717 Thermal correction to Enthalpy= 0.605661 Thermal correction to Gibbs Free Energy= 0.507169 Sum of electronic and ZPE= -1696.571736 Sum of electronic and thermal Energies= -1696.539651 Sum of electronic and thermal Enthalpies= -1696.538707 Sum of electronic and thermal Free Energies= -1696.637200 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.466 129.652 207.295 C,0.7593385777,-0.9469602073,0.6312571369 C,1.7651423783,-3.280610343,0.6390360459 C,-0.5073783233,-2.9211822365,-0.3738850862 C,0.3862153896,-3.8950082321,0.3955281792 C,-0.6135800678,-1.5978114513,0.3940477575 C,1.6477432655,-1.9506256475,1.3834579762 H,2.2633453316,-3.1148433406,-0.3254424544 H,-0.0862713644,-2.7381065256,-1.3649490121 H,-0.0765539582,-4.1412412152,1.3605177551 H,-1.0359056287,-1.8157347249,1.3781883782 H,1.1978846166,-2.1151714703,2.37178006 H,1.1934077472,-0.7131555236,-0.3498349017 H,2.3965925429,-3.9680415908,1.2106659444 H,-1.5129654936,-3.332618972,-0.5115188492 H,0.4759278704,-4.83104284,-0.1640175935 H,2.6338597707,-1.5094780048,1.553194136 N,-1.5204639131,-0.6688131131,-0.3055898894 N,0.5361069971,0.249189703,1.4349880981 C,1.428299279,1.1168196819,1.7089671985 C,-2.6752910764,-0.3555124976,0.1510449563 H,-3.2734547455,0.264486491,-0.5181718268 H,1.0862459498,1.9183094802,2.3733996423 C,-3.290878342,-0.7202771315,1.4423288876 C,-4.5801442864,-1.3135720927,3.8398132119 C,-2.6275064097,-0.5215265327,2.6598045396 C,-4.6120788488,-1.1801155344,1.4339612855 C,-5.2469885802,-1.4949776637,2.630120388 193 C,-3.2782809892,-0.8166268062,3.8529421824 H,-1.6184809147,-0.1158785009,2.6539281194 H,-5.1339774521,-1.2997711061,0.4886719326 H,-6.2652956113,-1.8692719902,2.6186260173 H,-2.7677959118,-0.6539597325,4.7965732642 H,-5.0804916728,-1.5474049856,4.7741612445 C,2.8542854248,1.2920389113,1.3293380949 C,5.526740131,1.907038783,0.7302523223 C,3.5557860322,2.2576441543,2.0641244169 C,3.5159405556,0.6426314264,0.2764273291 C,4.8385875329,0.9543730555,-0.0194746224 C,4.8818605152,2.5585817852,1.7781048986 H,3.0413453166,2.7895975215,2.8601721857 H,3.0052150352,-0.0873785555,-0.3371200669 H,5.3329329694,0.4512340182,-0.8441903181 H,5.405921111,3.3077482655,2.3627355856 H,6.5597228364,2.1425271276,0.4940929069 H,0.2374564488,-2.8177758386,-4.2905388935 C,-0.720931231,-2.3093024234,-4.3026050558 C,-3.2129841088,-0.9453883748,-4.3224253863 C,-0.9843319332,-1.2795997185,-3.4211275997 C,-1.7322775534,-2.6593513915,-5.2120610188 C,-2.9511371523,-1.9915256976,-5.2220455535 C,-2.2165311949,-0.6088085999,-3.4279958568 H,-1.5548491497,-3.4644923284,-5.9177851189 H,-3.7160335432,-2.2800985479,-5.9358063757 H,-4.1587811302,-0.4142681028,-4.3234889916 O,-2.2296472351,0.3668188526,-2.4821903016 O,-0.1663943832,-0.7564422672,-2.4702639938 B,-1.0091903627,0.1510802844,-1.6879514879 H,3.3500604637,3.5674400325,-1.1338152165 C,2.4239412375,3.900535927,-0.6776655327 C,-0.0172565887,4.7106713542,0.5671235343 C,1.27414411,3.1389268805,-0.755892114 C,2.3353318187,5.0927223304,0.0479038146 C,1.1421225052,5.4885633042,0.6566346562 C,0.0820067407,3.533558295,-0.1514754369 H,3.2161244221,5.7190934065,0.1438870322 H,1.1111303622,6.4203822358,1.2116821246 H,-0.9492344119,5.0074370381,1.0346397211 O,-0.873696892,2.5851707018,-0.386865873 O,1.0839138872,1.9297102362,-1.3681064511 B,-0.2476187024,1.579440555,-1.1298220717 194 IA-E,E[1,2]benzene (Intermediate monocoordinate 1,2-B2cat2-E,E-diimine 1 complex in benzene) E-coord_cydiimph2_EE_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1542449 Zero-point correction= 0.572565 (Hartree/Particle) Thermal correction to Energy= 0.604425 Thermal correction to Enthalpy= 0.605370 Thermal correction to Gibbs Free Energy= 0.509027 Sum of electronic and ZPE= -1696.581680 Sum of electronic and thermal Energies= -1696.549820 Sum of electronic and thermal Enthalpies= -1696.548875 Sum of electronic and thermal Free Energies= -1696.645218 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.283 129.893 202.771 C,-0.0755833508,-2.0789172179,-1.0025351826 C,1.5994976487,-3.8994479264,-1.6337148639 C,2.3702808629,-1.5181562025,-1.5544546783 C,2.506495038,-2.8550250221,-2.2842684986 C,0.9171902016,-1.0500220569,-1.5816572867 C,0.1416575941,-3.4448784975,-1.6723189334 H,1.9139290148,-4.0518492894,-0.5927791664 H,2.7127890609,-1.6630875335,-0.5278946715 H,2.2320742618,-2.7369056939,-3.3409281419 H,0.632179156,-0.9196802908,-2.6324645477 H,-0.1914389881,-3.3573919843,-2.7145260691 H,0.0797210187,-2.1652236518,0.0870473192 H,1.6960919493,-4.8645497045,-2.1404915746 H,3.0067681724,-0.7475708789,-2.0019634278 H,3.551179778,-3.17758291,-2.2571171538 H,-0.5161210931,-4.1736275271,-1.1884174415 N,-1.4135972921,-1.6252416385,-1.33569066 N,0.7161611094,0.257542046,-0.9078602532 C,-0.1494074823,1.0313673334,-1.465811442 H,-0.6452249128,0.6347329598,-2.3538907111 C,-2.2975872071,-1.5525617964,-0.425555679 H,-2.0860296474,-1.7988480195,0.6256740067 B,1.4373991418,0.5521581958,0.5531279979 B,1.9389502975,-0.73284549,1.5369497407 O,3.2711600737,-1.0105643725,1.7263438906 O,0.4408975528,1.2568853615,1.3621623472 C,3.8373672692,0.9104304341,0.3257335345 195 C,6.4948923609,-0.0161204936,0.3366727459 C,4.1861574707,-0.2737985164,1.0111016922 C,4.8480730327,1.6087220763,-0.3379673432 C,6.1637739416,1.1576060407,-0.3337810002 C,5.5010242637,-0.7238302475,1.0053055404 H,4.5662644734,2.5194191665,-0.856820165 H,6.9262482149,1.7246701584,-0.8578821107 H,5.7213004405,-1.6381361204,1.5470125719 H,7.516727286,-0.3796498989,0.3455194094 O,2.5821066979,1.4154136137,0.2814086985 C,-0.4865667113,0.4878240136,1.9748248103 C,-2.4466873043,-0.9969418893,3.3363934906 C,-0.1863125647,-0.7859669641,2.5109225775 C,-1.7838997654,0.9817143732,2.1224342972 C,-2.7549014959,0.252599309,2.8032069331 C,-1.1606488381,-1.5118161584,3.185605319 H,-1.9981145809,1.9597779244,1.7017546934 H,-3.7541207684,0.6627915937,2.9106435348 H,-0.8811846903,-2.4753474881,3.5998585775 H,-3.1964606523,-1.5678362818,3.874682427 O,1.0810204778,-1.3079509014,2.4480539469 C,-0.6012144366,2.3711103352,-1.0798829105 C,-1.645996814,4.8829917249,-0.4802105074 C,0.2115516802,3.3380109273,-0.4733315857 C,-1.9267367537,2.6832320514,-1.4111522261 C,-2.45547446,3.9280559856,-1.0907203481 C,-0.3141364656,4.5903407886,-0.1856629742 H,1.2434792558,3.1053791961,-0.23737468 H,-2.5487522898,1.9348036974,-1.896001134 H,-3.4896301292,4.1547448303,-1.3270512398 H,0.3165351891,5.34138929,0.2781497807 H,-2.0497764897,5.8619778571,-0.241433484 C,-3.6806812538,-1.1323487375,-0.734849781 C,-6.3026397703,-0.3389392168,-1.2809638433 C,-4.647114507,-1.1489527713,0.2728954608 C,-4.0401944503,-0.7252443155,-2.0259544283 C,-5.3427907105,-0.3264025927,-2.2949064353 C,-5.9546745054,-0.7545806252,0.0008558231 H,-4.3650650018,-1.4697109972,1.271554063 H,-3.285012144,-0.7372305988,-2.8059552235 H,-5.6165743489,-0.0104795355,-3.296732045 H,-6.7005458506,-0.7718258847,0.7891283177 H,-7.3208352597,-0.0287723451,-1.4940586993 196 IA-E,Z[1,2]benzene (Intermediate monocoordinate E-coordinated 1,2-B2cat2-E,Z-diimine 1 complex in benzene) E-coord_cydiimph2_EZ_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1422314 Zero-point correction= 0.573133 (Hartree/Particle) Thermal correction to Energy= 0.604738 Thermal correction to Enthalpy= 0.605682 Thermal correction to Gibbs Free Energy= 0.510322 Sum of electronic and ZPE= -1696.569098 Sum of electronic and thermal Energies= -1696.537493 Sum of electronic and thermal Enthalpies= -1696.536549 Sum of electronic and thermal Free Energies= -1696.631909 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.479 129.663 200.702 C,0.8200770303,-1.1326130103,1.7314849686 C,0.1368614936,-3.4388529011,2.557465265 C,-1.6278524444,-1.8182556414,1.7966203633 C,-1.2989511612,-2.9551081164,2.7656288323 C,-0.6303506465,-0.6749582042,1.9725094355 C,1.1256025994,-2.2830739214,2.7064783581 H,0.2294821886,-3.8737001844,1.5528306744 H,-1.5754327894,-2.2091675955,0.7764027393 H,-1.4191225905,-2.6067863739,3.7999961484 H,-0.6752109634,-0.3429796962,3.0166546264 H,1.0726923368,-1.874585463,3.7240245022 H,0.9060023169,-1.4785307115,0.6920249837 H,0.3830323464,-4.2309836921,3.2713003579 H,-2.6460586377,-1.4457043773,1.9470482605 H,-2.0070982397,-3.7756587359,2.6190656558 H,2.1564960541,-2.6195164347,2.559816329 N,1.6950974834,-0.0108225218,2.0109987581 N,-0.9705262869,0.4994483415,1.1349214182 C,-0.8103218204,1.6427139979,1.7052670117 H,-0.3685626559,1.6273519926,2.702527086 C,2.8765170294,0.0907555646,1.5491847086 H,3.4083965257,0.9949897148,1.8639897664 B,-1.3644691041,0.2607505193,-0.4505082279 B,-0.6291509903,-1.0170356243,-1.2797961265 O,-1.3565291484,-2.0963821278,-1.7218968059 O,-0.9201642177,1.4451695678,-1.1871579359 C,-3.396004688,-1.0290451284,-0.8753069268 197 C,-4.7622758061,-3.3935425531,-1.5673386815 C,-2.7048959372,-2.1222440825,-1.4453130184 C,-4.771889346,-1.1577451117,-0.6712929605 C,-5.4535325921,-2.3204040585,-1.0130205175 C,-3.3918689741,-3.2841240405,-1.7787463351 H,-5.2886832668,-0.3091998533,-0.2342975987 H,-6.5233625529,-2.3841436145,-0.8425670522 H,-2.8187685229,-4.0952128716,-2.2165676293 H,-5.2803814583,-4.3072251388,-1.8378625914 O,-2.8155148901,0.1347686595,-0.5034051997 C,0.4049388391,1.5232647868,-1.4534904501 C,3.1295934873,1.7808931587,-2.0694573361 C,1.1853809709,0.3841964257,-1.7554375486 C,1.0186035223,2.7763875017,-1.4627462996 C,2.3700316613,2.9080092387,-1.7700558326 C,2.5315121148,0.5230016521,-2.0670160099 H,0.3998447658,3.639343233,-1.233112124 H,2.8251684473,3.8933832725,-1.7758630342 H,3.0982400891,-0.3738254637,-2.3007194574 H,4.1839818801,1.8714915533,-2.3099141044 O,0.6207931098,-0.8676312858,-1.8388540801 C,-1.1551534963,2.9765254082,1.209813122 C,-1.7230842402,5.5844256616,0.4196025177 C,-2.2587254426,3.2299548607,0.3849721492 C,-0.365236804,4.0392389682,1.6663043506 C,-0.6344739585,5.3387344398,1.254046087 C,-2.5395344587,4.5339471295,-0.0005040433 H,-2.8864960756,2.4086931328,0.0566280979 H,0.4745710239,3.8352195552,2.3252238137 H,-0.0061825834,6.1567078323,1.590115426 H,-3.395470404,4.7325880872,-0.6366893507 H,-1.9447850762,6.5994875548,0.1050558533 C,3.7058875794,-0.7427350179,0.6401962165 C,5.4304291124,-2.0300213826,-1.1715204631 C,4.9036840395,-0.1424189331,0.2236262885 C,3.4006917592,-2.0201571566,0.1442009033 C,4.2560114094,-2.6511388143,-0.7541903716 C,5.7571188848,-0.7706725444,-0.6736608561 H,5.1515993363,0.8475282391,0.5973190718 H,2.5058824871,-2.5451260304,0.4475539723 H,3.9984723951,-3.6357353716,-1.1305447279 H,6.6728360045,-0.2788979242,-0.9857801665 H,6.0897719464,-2.5277233388,-1.8754732559 198 IA-Z,E[1,2]benzene (Intermediate monocoordinate Z-coordinated 1,2-B2cat2-Z,E-diimine 1 complex in benzene) Z-coord_cydiimph2_ZE_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1530035 Zero-point correction= 0.572497 (Hartree/Particle) Thermal correction to Energy= 0.604428 Thermal correction to Enthalpy= 0.605372 Thermal correction to Gibbs Free Energy= 0.508240 Sum of electronic and ZPE= -1696.580507 Sum of electronic and thermal Energies= -1696.548575 Sum of electronic and thermal Enthalpies= -1696.547631 Sum of electronic and thermal Free Energies= -1696.644763 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.284 129.925 204.432 C,0.2315486135,-0.0029516508,1.8157104245 C,-1.2513486943,0.1277671672,3.8875759879 C,-2.185828671,0.8653317879,1.6841901074 C,-2.1657754669,1.1337723834,3.1887730108 C,-0.7709733705,0.935219765,1.111966374 C,0.1696843585,0.2185889938,3.3347620159 H,-1.6458072138,-0.8854879552,3.7340374627 H,-2.6138426593,-0.1271882478,1.5209368853 H,-1.8058444859,2.1528679813,3.3832306302 H,-0.3775564453,1.9426619128,1.2648049585 H,0.586403234,1.2126333643,3.5416085561 H,-0.0148838141,-1.0538389064,1.582846017 H,-1.2373111368,0.3043835053,4.967463537 H,-2.8268799499,1.5797927944,1.1556458099 H,-3.1842684466,1.0711037137,3.5824828415 H,0.8310039469,-0.5102001304,3.8139307943 N,1.5584534604,0.3681573598,1.3610564047 N,-0.7395447618,0.6258532058,-0.328459882 C,-0.0807801267,1.3343542108,-1.1681875359 H,-0.0162515703,0.9080836154,-2.1705355098 C,2.3662289649,-0.5368762615,0.9834673287 H,2.0895699527,-1.6017319989,0.9490137152 B,-1.5168194358,-0.6976330831,-0.9760659515 B,-2.0352466137,-1.9752827851,-0.0047191357 O,-3.3612553572,-2.1336363114,0.3144644746 O,-0.5633230398,-1.2615593045,-1.9339267376 C,-3.8859183009,-0.221427786,-1.1178968605 199 C,-6.4841200387,-0.2767076595,-0.0338733785 C,-4.2400409671,-1.1737862956,-0.135441389 C,-4.8639177682,0.6827347491,-1.5380788175 C,-6.1499302851,0.658571787,-1.0087239242 C,-5.5240778365,-1.1879019802,0.39549809 H,-4.5799054869,1.4035576838,-2.2980739721 H,-6.8870726258,1.3738537724,-1.359036859 H,-5.7493987161,-1.9387603748,1.1461065498 H,-7.4829716813,-0.3044897898,0.3879669296 O,-2.6603147104,-0.1413234606,-1.6840120684 C,0.3170508253,-2.1657987444,-1.4442426993 C,2.1944216917,-4.0688008835,-0.5620713521 C,0.0091172559,-3.0478719683,-0.3807312136 C,1.5774564933,-2.262593995,-2.0367932983 C,2.506042935,-3.2076965022,-1.6111901691 C,0.9452939387,-3.9820387151,0.0478287598 H,1.8005110152,-1.5840508798,-2.8542580299 H,3.4745160074,-3.262528082,-2.0981968163 H,0.660872339,-4.6467264859,0.8573119532 H,2.9104214596,-4.8107575133,-0.2240211241 O,-1.2255969068,-3.0653788131,0.2192296445 C,0.5997766354,2.6258943091,-0.9601192997 C,1.9412709735,5.0564429911,-0.7240003554 C,-0.0383504702,3.7234807367,-0.3717957949 C,1.8983005864,2.7617276529,-1.460743867 C,2.5736630616,3.9697939013,-1.3236691107 C,0.6326569622,4.9355226744,-0.2594753535 H,-1.06482437,3.63229506,-0.0281273941 H,2.3828014197,1.9125702362,-1.9352031748 H,3.5893422982,4.0632248347,-1.694142162 H,0.1325029162,5.7878599017,0.1880799161 H,2.4633052194,6.0031399121,-0.6292921755 C,3.7475783338,-0.2034956356,0.5762342899 C,6.3623214192,0.3978297537,-0.1980488972 C,4.6348183672,-1.2267405704,0.2357643742 C,4.1829559049,1.1272244078,0.5399154086 C,5.4820604588,1.4243273973,0.1495884391 C,5.9390581841,-0.9274034215,-0.1499122418 H,4.2941434569,-2.2575323272,0.2737188853 H,3.4863826098,1.9101969662,0.8226136334 H,5.8147641966,2.4575551174,0.1208233431 H,6.623750728,-1.7276934152,-0.412202382 H,7.3780291995,0.6327643286,-0.50085762 200 IA-Z,Z[1,2]benzene (Intermediate monocoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in benzene) Z-coord_cydiimph2_ZZ_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.140699 Zero-point correction= 0.573165 (Hartree/Particle) Thermal correction to Energy= 0.604861 Thermal correction to Enthalpy= 0.605805 Thermal correction to Gibbs Free Energy= 0.509946 Sum of electronic and ZPE= -1696.567534 Sum of electronic and thermal Energies= -1696.535838 Sum of electronic and thermal Enthalpies= -1696.534894 Sum of electronic and thermal Free Energies= -1696.630753 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.556 129.580 201.753 C,-1.0840843732,-0.8167315566,0.1913927191 C,-2.7171056525,-0.9426041442,2.1321887491 C,-0.2967063732,-0.4202537013,2.5729623655 C,-1.5564969068,-1.0952562883,3.1169259104 C,0.0597752779,-1.0046976966,1.2088161488 C,-2.343679872,-1.4935125355,0.7559429164 H,-2.975438574,0.1214616231,2.0425032954 H,-0.4877306485,0.6538525324,2.4772757133 H,-1.3602169802,-2.1625053299,3.2849847763 H,0.2056245099,-2.0832146138,1.3036332589 H,-2.1385216421,-2.5695616343,0.8237360431 H,-1.2563367695,0.2615752343,0.0663725435 H,-3.6080676759,-1.4557761492,2.5070018219 H,0.5486202324,-0.5332449538,3.2598897714 H,-1.8156901932,-0.659870145,4.0862388842 H,-3.1672171796,-1.3755265586,0.0448215468 N,-0.687005286,-1.4552160045,-1.0477414605 N,1.2878307294,-0.416018594,0.6505808091 C,2.1861317449,-1.144507557,0.1008132326 H,2.982581291,-0.5908330461,-0.3966340587 C,-1.1955509426,-1.1767899698,-2.1801123516 H,-0.7896361002,-1.7636196394,-3.0115953799 B,1.5261629599,1.2216244977,0.666820141 B,0.2148256292,2.2585208269,0.4524140362 O,-0.248036877,3.0527018754,1.472386071 O,2.4189411936,1.4853500964,-0.4685741658 C,1.5985559375,2.2498055408,2.8753594625 201 C,0.4727522863,3.7484159466,4.9802662464 C,0.409321686,2.9897774567,2.6815341658 C,2.1960321618,2.2913508007,4.1377426822 C,1.6483561784,3.0308642122,5.1799136078 C,-0.1363329731,3.7217388895,3.7300519273 H,3.1099717624,1.7211653456,4.270134087 H,2.1418861345,3.0416713087,6.1463796753 H,-1.0482958321,4.2756562534,3.5313177377 H,0.0329938216,4.3284545135,5.7843606475 O,2.1940381852,1.4900641581,1.9293929005 C,1.8102092624,1.5487360133,-1.6801055777 C,0.6575322234,1.6721781244,-4.2400504815 C,0.5035138919,2.0605454877,-1.8590714014 C,2.5068798599,1.1027851292,-2.8041494611 C,1.9419023107,1.163393006,-4.0751997866 C,-0.0520483493,2.1241139758,-3.1305437037 H,3.5140762564,0.7251921125,-2.6538936436 H,2.5095812263,0.815131066,-4.9321516096 H,-1.0566806001,2.5264971714,-3.2260926475 H,0.2040324062,1.7246420564,-5.2244656917 O,-0.2246461997,2.5765928834,-0.8129360131 C,2.2765644932,-2.6190174632,0.0730460886 C,2.5830062092,-5.3835069892,-0.0571864188 C,2.3182174546,-3.3734607039,1.2490793043 C,2.4116302651,-3.2493505847,-1.1667958253 C,2.5485913651,-4.6311814248,-1.2298103236 C,2.4755512942,-4.7538850984,1.180541147 H,2.2457441995,-2.8756407029,2.2122735198 H,2.3888091982,-2.6525167767,-2.0743647782 H,2.6359608238,-5.121104074,-2.1939184713 H,2.5165461879,-5.336695074,2.0948291321 H,2.701235082,-6.4610589253,-0.1080861844 C,-2.2148366422,-0.1999378405,-2.6464284194 C,-3.9744281337,1.6483983436,-3.8312751688 C,-2.3641769827,-0.1264227765,-4.0398922814 C,-2.9887162958,0.6628056274,-1.853998517 C,-3.8537351416,1.5786564306,-2.4457861889 C,-3.2294656141,0.7845924412,-4.6310282911 H,-1.76921589,-0.7856828053,-4.6662833915 H,-2.9378970213,0.6373313859,-0.7744432926 H,-4.4365099393,2.2423737174,-1.815538975 H,-3.3195369879,0.8239412945,-5.7118405969 H,-4.6499411125,2.3672439885,-4.2839285176 202 IB-E,E[1,1]MeOH (Intermediate dicoordinate 1,1-B2cat2-E,E-diimine 1 complex in MeOH) cfc_boat_cydiimph2_EE_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1521442 Zero-point correction= 0.571577 (Hartree/Particle) Thermal correction to Energy= 0.603169 Thermal correction to Enthalpy= 0.604113 Thermal correction to Gibbs Free Energy= 0.508368 Sum of electronic and ZPE= -1696.580567 Sum of electronic and thermal Energies= -1696.548975 Sum of electronic and thermal Enthalpies= -1696.548031 Sum of electronic and thermal Free Energies= -1696.643776 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.494 129.843 201.512 H,-3.2638233592,2.7291071128,-1.209622292 C,-2.450098532,3.0447672335,-0.5486426649 C,-0.9629431951,4.9754027182,0.1171070301 C,-0.0365982117,2.6609814285,0.0327925456 C,0.2687334879,4.1340705261,-0.2291922205 C,-1.1988359112,2.2232045209,-0.8762855564 C,-2.169995721,4.539297655,-0.7147654339 H,-1.1906866184,4.8619724589,1.1844743213 H,-0.3518570726,2.5623558856,1.0765036956 H,0.5182028124,4.2950509867,-1.285001162 H,-0.8931182414,2.4238264345,-1.9109244464 H,-1.9748603946,4.7538510951,-1.7733988615 H,-2.752251668,2.824664752,0.4815658315 H,-0.7437505389,6.0329904316,-0.0564299512 H,1.1335735949,4.4365289156,0.3705835121 H,-3.0580208205,5.1109332584,-0.4289409903 N,1.112533919,1.7355548829,-0.0909400918 N,-1.4678024918,0.7646015938,-0.7770772658 C,2.1173581388,2.0458362917,-0.8207728479 H,2.0773224839,2.9569437598,-1.4190591916 C,-2.0895573332,0.2420224555,-1.7679485725 H,-2.4203095063,0.9184975778,-2.5619106968 B,0.7948195127,0.2484035762,0.6050803652 B,-0.9261433731,0.0928776091,0.652424134 O,-1.7240087974,0.8317368899,1.6826090213 O,-1.4218568818,-1.2883975071,0.7383822923 O,1.5110939449,0.1355576044,1.901593344 203 O,1.4142172569,-0.7884062091,-0.2668356927 C,-2.6418263048,-1.210316692,1.3308984619 C,-4.9726613601,-0.6102326006,2.678877761 C,-3.6188381814,-2.1835789956,1.4050158184 C,-2.820500067,0.0573736416,1.905112821 C,-3.9772153226,0.3788530413,2.5884043859 C,-4.79936496,-1.8620032588,2.0975225249 H,-3.4708182607,-3.1549989015,0.9428304124 H,-4.1067097831,1.3601293756,3.0340465743 H,-5.5874712146,-2.6045012802,2.1749308458 H,-5.8940718218,-0.3861932536,3.2073911047 C,2.3698715823,-1.4065868782,0.4698309891 C,4.2148849918,-2.3406647134,2.2980997419 C,3.2241102286,-2.4160685491,0.0749902419 C,2.4266534082,-0.8594184154,1.7610584452 C,3.3403995108,-1.311263768,2.6921818868 C,4.1593716089,-2.880168032,1.0178644314 H,3.1773189362,-2.8208735931,-0.9311218946 H,3.382678934,-0.8765877678,3.6857405 H,4.8452671659,-3.673750094,0.7378880434 H,4.9435293598,-2.7168825573,3.0095560928 C,3.3769732084,1.2788140491,-0.8682633928 C,5.8277118915,-0.0388495356,-0.9536399139 C,3.8472832494,0.7637102948,-2.080231706 C,4.1419860379,1.1524236286,0.2942878476 C,5.375497787,0.5058007066,0.2447945687 C,5.0597747034,0.0839899672,-2.1135834517 H,3.2556994705,0.8813513345,-2.9835270872 H,3.7748048828,1.573063072,1.2257229716 H,5.9719938392,0.4164401954,1.147365195 H,5.4143893041,-0.3390199955,-3.0480786821 H,6.7811786636,-0.5568206869,-0.9886931646 C,-2.4040624257,-1.1812696694,-1.982928618 C,-3.064727824,-3.8306352763,-2.5239654664 C,-1.4255165921,-2.1762444325,-1.884475045 C,-3.7011419358,-1.5097164137,-2.3890510229 C,-4.035950054,-2.8380246517,-2.6366708304 C,-1.7588810912,-3.4967030492,-2.1610934904 H,-0.4147460538,-1.9072393787,-1.5939683729 H,-4.4473009175,-0.7266652948,-2.4932872345 H,-5.049270339,-3.0945428759,-2.9282558222 H,-0.9995223657,-4.2689859076,-2.0906479232 H,-3.3208657522,-4.8653567403,-2.7300746007 204 IB-E,Z[1,1]MeOH (Intermediate dicoordinate 1,1-B2cat2-E,Z-diimine 1 complex in MeOH) boat_cydiimph2_EZ_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1475808 Zero-point correction= 0.571633 (Hartree/Particle) Thermal correction to Energy= 0.603420 Thermal correction to Enthalpy= 0.604364 Thermal correction to Gibbs Free Energy= 0.506600 Sum of electronic and ZPE= -1696.575948 Sum of electronic and thermal Energies= -1696.544161 Sum of electronic and thermal Enthalpies= -1696.543217 Sum of electronic and thermal Free Energies= -1696.640981 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.652 129.665 205.762 H,1.1116469277,-3.3335963829,1.4768276114 C,0.3604615605,-2.6460035006,1.8798092915 C,-1.8820975458,-2.4887334772,3.0554813736 C,-1.3033192832,-0.86757401,1.2753570874 C,-2.4486536377,-1.6729959433,1.8869988604 C,-0.2286265185,-1.824951865,0.7307289866 C,-0.7590735168,-3.4183203621,2.5856751552 H,-1.4963150208,-1.8061085913,3.8232977953 H,-0.8558328176,-0.2850566768,2.0892614105 H,-2.8870909658,-2.3558751692,1.1536724974 H,-0.7251512804,-2.5081688148,0.0322723835 H,-1.1750139677,-4.1615925555,1.8930158561 H,0.8617976086,-1.9721958929,2.5818816037 H,-2.6852002763,-3.0717664325,3.5158840938 H,-3.2348710428,-0.9904961635,2.2254109206 H,-0.3421263597,-3.9686487112,3.43444725 N,-1.6109655044,0.1500223637,0.2524069623 N,0.7957158348,-1.0793387332,-0.0466188123 C,-2.5131145274,0.1019771404,-0.6489258685 H,-2.5566251624,0.9727183081,-1.3056413745 C,1.3699037339,-1.7385068604,-0.9836211223 H,1.1229503601,-2.8013945718,-1.0682565732 B,-0.4622904958,1.3455208326,0.3187902708 B,1.0439268865,0.5057552606,0.4870429791 O,1.5032336244,0.2842486975,1.8926365883 O,2.22321185,1.0388525867,-0.2006658099 O,-0.83929237,2.1859041401,1.4894832582 205 O,-0.6655859385,2.210110627,-0.8611164508 C,3.2912657574,0.6665781143,0.5544283316 C,5.1269743706,-0.1597727562,2.4388910129 C,4.6290881808,0.6957124178,0.213735154 C,2.8602902277,0.2203402108,1.8128850832 C,3.7618929877,-0.1947449958,2.7737963366 C,5.5514098192,0.2728948731,1.1867978895 H,4.9446754467,1.0325659384,-0.7691462907 H,3.422686302,-0.5344079192,3.7473272412 H,6.6112074621,0.2822925065,0.9520539891 H,5.8594001757,-0.4825156281,3.1722475137 C,-1.372033374,3.2909907806,-0.421864575 C,-2.7094482817,5.3102522096,0.9005979856 C,-1.9228476195,4.3094234167,-1.1740839417 C,-1.4801530211,3.2689852707,0.9767632924 C,-2.1459360654,4.2696512609,1.6586957524 C,-2.6005111026,5.3304432761,-0.4856225272 H,-1.82991956,4.3143601534,-2.2553727683 H,-2.2241855675,4.2460471122,2.7408250402 H,-3.0448414783,6.144742484,-1.0492857887 H,-3.238391328,6.1094961468,1.4103593426 C,-3.4613887272,-1.0043883203,-0.9163544227 C,-5.2461848232,-3.0729327329,-1.4420896017 C,-4.8059528003,-0.8665029535,-0.5650268228 C,-3.0147265958,-2.159907862,-1.5632173723 C,-3.9111273228,-3.1933820304,-1.8230875735 C,-5.6926495512,-1.9090808151,-0.8177295872 H,-5.1471181931,0.0427449765,-0.0789536593 H,-1.9735479602,-2.243266875,-1.8632532525 H,-3.565015905,-4.0923925483,-2.3229572221 H,-6.7341028212,-1.8111005368,-0.5283399838 H,-5.9414199948,-3.8827069821,-1.6397623493 C,2.3083125428,-1.2287703726,-1.9970902538 C,4.0658054517,-0.4126073146,-3.9955960322 C,2.0381479119,-0.068600885,-2.7314748548 C,3.438988924,-1.9972631094,-2.2910291065 C,4.3290037228,-1.5755241653,-3.2746396685 C,2.9148472205,0.332059417,-3.7320000604 H,1.1439527682,0.5081449465,-2.5155366864 H,3.6249279322,-2.9141402351,-1.738368549 H,5.2182870482,-2.1604324977,-3.4858212911 H,2.7026731535,1.2278675535,-4.3066552457 H,4.751216532,-0.0906297726,-4.7735127023 206 IB-Z,E[1,1]MeOH (Intermediate dicoordinate 1,1-B2cat2-Z,E-diimine 1 complex in MeOH) boat_cydiimph2_ZE_b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1538641 Zero-point correction= 0.571943 (Hartree/Particle) Thermal correction to Energy= 0.603434 Thermal correction to Enthalpy= 0.604378 Thermal correction to Gibbs Free Energy= 0.508560 Sum of electronic and ZPE= -1696.581921 Sum of electronic and thermal Energies= -1696.550431 Sum of electronic and thermal Enthalpies= -1696.549486 Sum of electronic and thermal Free Energies= -1696.645304 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.660 129.527 201.666 H,-2.8947410489,1.6623527876,-2.0300681195 C,-2.6257991281,1.9054929764,-0.9966673919 C,-2.2212793952,3.7793519504,0.6509296465 C,-0.7827487364,1.7459413263,0.7108978441 C,-0.7981938886,3.2621965092,0.8835919142 C,-1.2025640682,1.4023160899,-0.7292741091 C,-2.7133040668,3.4123300589,-0.7504032688 H,-2.8919770632,3.3442474828,1.4025028747 H,-1.5147637215,1.3170054434,1.4029101065 H,-0.1286977696,3.7410379356,0.1584061723 H,-0.5074092175,1.9129742361,-1.4012141988 H,-2.1000355544,3.9340485665,-1.4963606537 H,-3.3158537653,1.367162079,-0.3360959363 H,-2.2423812876,4.8643943769,0.7881774136 H,-0.4447912405,3.5176369683,1.8880070813 H,-3.7455999408,3.7458881688,-0.8921947866 N,0.4887464713,1.0648045199,1.044056937 N,-1.1359551714,-0.0514721891,-0.9697047218 C,1.5958491492,1.7044905999,0.9841516631 H,1.5926976961,2.7355791921,0.6282947724 C,-0.9139638394,-0.5435133167,-2.1302002193 H,-0.9630362104,-1.6308449002,-2.1943650859 B,0.2935986391,-0.5925971327,1.1937256092 B,-1.1846532622,-0.9932779922,0.3800126152 O,-2.4993489704,-0.7350318531,1.0330693539 O,-1.2594479466,-2.3974538628,-0.0814208401 O,0.401287489,-0.9956299692,2.6174925412 207 O,1.4611520816,-1.2256210639,0.5221037964 C,-2.5746749259,-2.7462300726,-0.015888847 C,-5.2909451214,-3.0537806722,0.3729353922 C,-3.1749716785,-3.8978125067,-0.4857992754 C,-3.3125546409,-1.7535610129,0.6453318988 C,-4.6725935366,-1.8851140305,0.8496024603 C,-4.5581710691,-4.039019192,-0.2800905392 H,-2.5930234275,-4.6605837202,-0.9931085902 H,-5.2343707534,-1.111228823,1.3629129927 H,-5.0583961932,-4.9327621868,-0.6396927603 H,-6.3586961652,-3.184715434,0.5184343182 C,2.1395747891,-1.9110483492,1.4751144185 C,3.2090280605,-3.1193346007,3.7160509652 C,3.3068784798,-2.633885548,1.3316439422 C,1.5070555201,-1.7803998338,2.7215011359 C,2.0208833893,-2.3783795884,3.8546779441 C,3.8394735212,-3.2422478404,2.4830187445 H,3.7945359929,-2.7142597463,0.3652617227 H,1.5277379131,-2.2659302574,4.8149264384 H,4.756483337,-3.817747546,2.4020580586 H,3.6370974442,-3.600949531,4.5897789252 C,2.8981073773,1.1566568899,1.408885473 C,5.3887985416,0.2380807889,2.2459898478 C,3.9559501818,1.0859950958,0.4965484075 C,3.0925749213,0.7878689157,2.7422459219 C,4.3451023326,0.3429002642,3.1611377258 C,5.1914481078,0.6026334891,0.9125161623 H,3.8020566944,1.3915593287,-0.5345713468 H,2.2688011152,0.8638062585,3.4457831392 H,4.4969989006,0.0654996384,4.1995532895 H,6.0061415893,0.5224737066,0.19995577 H,6.3598562715,-0.1236280132,2.5698150196 C,-0.5928136899,0.2063783128,-3.3633514776 C,0.0299879516,1.5190298202,-5.7395796473 C,0.5630607552,0.9909055995,-3.4456157634 C,-1.4207417681,0.0583488398,-4.4799631334 C,-1.1152555405,0.7286972685,-5.6609357233 C,0.8724855563,1.6417222019,-4.6356584876 H,1.2240298165,1.0690259102,-2.586057823 H,-2.3028027235,-0.5724645774,-4.4166881658 H,-1.7669886743,0.6253639293,-6.5225116614 H,1.7740565788,2.2422381115,-4.7015153568 H,0.2720085361,2.0320897452,-6.6650125455 IB-Z,Z[1,1]MeOH (Intermediate dicoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in MeOH) boat_cydiimph2_ZZ_b2cat2_meoh 208 M062X/6-31G(d,p) E(RM062X) = -1697.1491688 Zero-point correction= 0.572515 (Hartree/Particle) Thermal correction to Energy= 0.604074 Thermal correction to Enthalpy= 0.605018 Thermal correction to Gibbs Free Energy= 0.507728 Sum of electronic and ZPE= -1696.576654 Sum of electronic and thermal Energies= -1696.545095 Sum of electronic and thermal Enthalpies= -1696.544151 Sum of electronic and thermal Free Energies= -1696.641441 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.062 129.238 204.765 H,2.481344816,1.9668404814,-1.6818111144 C,1.6211563299,1.3989011294,-2.0519837845 C,-0.3647870215,1.434700241,-3.6257137294 C,-0.5786593329,0.3871699485,-1.3910256151 C,-1.3159394644,1.2081497266,-2.4451276377 C,0.6620358911,1.1411641298,-0.8840428049 C,0.9032974166,2.1608782934,-3.1690371466 H,-0.0952740553,0.4688473181,-4.0715918894 H,-0.2239760825,-0.5173443034,-1.9018232125 H,-1.6251350931,2.1797595652,-2.0545640478 H,0.3385205787,2.0997983722,-0.4731634381 H,0.6337887991,3.16136586,-2.806084729 H,1.9889712304,0.4349915264,-2.4215810177 H,-0.8755007898,2.016739816,-4.3985081792 H,-2.2165402042,0.6694644356,-2.7570517815 H,1.5882021132,2.2986569376,-4.0110922796 N,-1.3282813653,-0.1511268371,-0.2441496703 N,1.3372792113,0.3700728641,0.181158537 C,-2.3611039774,0.3130967923,0.3518394426 H,-2.7394008776,-0.3332289329,1.1456151634 C,2.0260610757,0.9467162059,1.0913558111 H,2.5363558278,0.283923608,1.7902780012 B,-0.5987536609,-1.5676270437,0.2318786498 B,1.1123495302,-1.277929812,0.1652234261 O,1.7743073189,-1.736992482,-1.0917184393 O,1.9486638723,-1.8194973527,1.2549357986 O,-1.0732198632,-2.5818403908,-0.7565488155 O,-1.206792149,-1.9697537919,1.5155269376 C,3.1240398263,-2.1962777592,0.6734658913 C,5.2696168676,-2.9004943711,-0.9136475761 209 C,4.2886432664,-2.6025129683,1.2943728448 C,3.0185896841,-2.1405660854,-0.7241978672 C,4.080462492,-2.4871298342,-1.5378967348 C,5.3719656569,-2.9574481516,0.472229514 H,4.3566100249,-2.6430753751,2.3767803333 H,3.9894747089,-2.4415077028,-2.6184551849 H,6.301805484,-3.2788520671,0.9308563648 H,6.1208134164,-3.1778711716,-1.5276249818 C,-2.1452484288,-2.9129722896,1.2166968436 C,-3.8594159683,-4.810168487,0.1789410087 C,-3.067220787,-3.4923071036,2.0658287967 C,-2.0694464096,-3.2672772656,-0.1385820446 C,-2.9186965718,-4.2145237123,-0.6787034742 C,-3.9325307742,-4.4574215155,1.5221123539 H,-3.1140982286,-3.2086496132,3.1123449199 H,-2.8530170383,-4.4843221247,-1.7277993573 H,-4.668365417,-4.9310001042,2.1644125386 H,-4.5388784797,-5.5575838728,-0.2187454948 C,-3.1352236704,1.5528623855,0.1522588468 C,-4.7627481893,3.8089969072,-0.0744742457 C,-4.5300079109,1.4215539597,0.1597220028 C,-2.5618121803,2.8267070725,0.0737091123 C,-3.3766037777,3.9490991563,-0.0348122435 C,-5.3392354856,2.5435437043,0.0215008343 H,-4.9730738782,0.4347974798,0.2622980253 H,-1.4847812951,2.9479823958,0.1174928292 H,-2.9260670772,4.9350776859,-0.0853316313 H,-6.4184063874,2.431428107,0.00497335 H,-5.3939193695,4.687440259,-0.1651692527 C,2.173643799,2.4069394208,1.284992821 C,2.4853913879,5.1395350333,1.7169671046 C,1.0735081529,3.1833604166,1.6632433647 C,3.434634034,2.9931349306,1.1488586062 C,3.5834763859,4.3624803788,1.3528385188 C,1.2332131495,4.5484908845,1.8797214634 H,0.1041597534,2.7115015769,1.8022109189 H,4.2887707773,2.3800602203,0.8758887018 H,4.559990063,4.8207323008,1.2336122606 H,0.379370857,5.1489077465,2.1774134552 H,2.6068974632,6.2053972478,1.8824530284 IB-E,E[1,2]MeOH (Intermediate dicoordinate 1,2-B2cat2-E,E-diimine 1 complex in MeOH) boat_cydiimph2_EE_1-2-b2cat2_meoh M062X/6-31G(d,p) 210 E(RM062X) = -1697.1660253 Zero-point correction= 0.572346 (Hartree/Particle) Thermal correction to Energy= 0.603503 Thermal correction to Enthalpy= 0.604447 Thermal correction to Gibbs Free Energy= 0.509582 Sum of electronic and ZPE= -1696.593679 Sum of electronic and thermal Energies= -1696.562523 Sum of electronic and thermal Enthalpies= -1696.561578 Sum of electronic and thermal Free Energies= -1696.656443 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.704 129.177 199.660 H,-2.530952109,2.1557629639,-2.3876436777 C,-2.3039257145,2.4133157052,-1.3480891299 C,-1.9152791179,4.3197498305,0.2674511949 C,-0.5945250532,2.2141860069,0.4623058285 C,-0.5421904064,3.7345350201,0.6051727331 C,-0.9314941448,1.8358174917,-0.9802575491 C,-2.3331372625,3.9298467757,-1.1508441601 H,-2.6551945553,3.9441107744,0.9855515201 H,-1.3963406534,1.8459319732,1.1123304314 H,0.2022858114,4.1625237617,-0.076511585 H,-0.1610942765,2.2691270958,-1.6328126065 H,-1.6478024314,4.3971857976,-1.8697999326 H,-3.0582562233,1.9277998623,-0.7155278857 H,-1.8874648287,5.4084527778,0.3707131082 H,-0.2439442886,3.9855508868,1.6279806685 H,-3.3363325035,4.3063510754,-1.3721169678 N,0.6133997668,1.4961199752,0.9155573541 N,-0.9396499504,0.3664914716,-1.2023687921 C,1.7753671031,1.9948937461,0.6894888418 H,1.84021945,2.9032158874,0.0887002121 C,-0.8025035714,0.0164302667,-2.4351374392 H,-0.5037624008,0.7967144481,-3.1409227802 B,0.1650481166,-0.0058504939,1.3344345389 B,-0.9511887344,-0.5885241937,0.12866752 O,-2.3477827639,-0.5720887587,0.5753916933 O,-0.4623909065,0.1518652681,2.6556964548 O,-0.5880216287,-1.9598711552,-0.2478507086 O,1.3322190619,-0.8665193994,1.4792641343 C,-1.6788934093,-0.3920132268,2.9125417847 C,-4.2001384073,-1.4202284283,3.6048728278 C,-2.0427252529,-0.5693828564,4.2484149416 211 C,-2.6016290593,-0.7439608758,1.9016495832 C,-3.8468556891,-1.254634671,2.2676166887 C,-3.29094064,-1.0767105061,4.601262784 H,-1.3156967258,-0.2902203967,5.0058046678 H,-4.5355831004,-1.5145021267,1.4685906829 H,-3.5454434673,-1.2007256449,5.6491594985 H,-5.1774647764,-1.817590782,3.8598017608 C,1.7001106731,-1.6582217549,0.443228547 C,2.4917058375,-3.4312128902,-1.5718358021 C,3.0475104468,-1.966210747,0.2615995648 C,0.7339145242,-2.2306554855,-0.4107017157 C,1.1421302897,-3.1177071555,-1.4052580257 C,3.4459164467,-2.8492873177,-0.7422790557 H,3.7710016884,-1.5118099302,0.9344563756 H,0.3790729218,-3.5625322905,-2.0389363578 H,4.4989261063,-3.0819571963,-0.8672801446 H,2.7894748575,-4.1261681085,-2.3508783471 C,3.0490161743,1.4749325704,1.1962661007 C,5.5283511913,0.608380259,2.1223051366 C,3.169138058,0.9593104829,2.4930234408 C,4.1812549277,1.58767915,0.380791402 C,5.414553903,1.1328636149,0.8352738142 C,4.4095794072,0.5348059108,2.953828335 H,2.2938291451,0.9090244973,3.1332314471 H,4.0853133558,2.0176082848,-0.6126317843 H,6.2870531644,1.2004503029,0.1936083793 H,4.5058124354,0.1447547641,3.9619572938 H,6.4939356469,0.2692473349,2.4848767928 C,-1.0638001222,-1.2917721809,-3.0314823918 C,-1.5534685953,-3.7148800784,-4.3106832964 C,-0.3209597489,-1.6515494849,-4.1634237879 C,-2.0870413336,-2.1301594818,-2.5697761804 C,-2.3298949785,-3.3370627534,-3.2137168281 C,-0.5500817399,-2.8717602453,-4.7880348463 H,0.4468100446,-0.9785296631,-4.5356890041 H,-2.6902257623,-1.8233980247,-1.7214565696 H,-3.1263142871,-3.9851411572,-2.8626094747 H,0.0416159912,-3.1598952857,-5.6507262887 H,-1.7441759463,-4.6623012569,-4.8055849486 IB-E,Z[1,2]MeOH (Intermediate dicoordinate 1,2-B2cat2-E,Z-diimine 1 complex in MeOH) boat_cydiimph2_EZ_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1602787 212 Zero-point correction= 0.572651 (Hartree/Particle) Thermal correction to Energy= 0.603856 Thermal correction to Enthalpy= 0.604800 Thermal correction to Gibbs Free Energy= 0.509437 Sum of electronic and ZPE= -1696.587627 Sum of electronic and thermal Energies= -1696.556422 Sum of electronic and thermal Enthalpies= -1696.555478 Sum of electronic and thermal Free Energies= -1696.650842 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.925 129.073 200.710 H,-2.0884633226,1.5943666894,-2.3190711984 C,-1.9362296645,1.8775064694,-1.2724086812 C,-1.6354451202,3.830821963,0.3156974639 C,-0.3632023414,1.7327207458,0.6582025432 C,-0.2862856779,3.2559223839,0.7588203336 C,-0.5940006232,1.3081942039,-0.7969812618 C,-1.9633547138,3.4001215192,-1.1155942436 H,-2.4226900628,3.4803932573,0.995390586 H,-1.2436705364,1.4254728818,1.2352690714 H,0.5026425763,3.6556440035,0.1150645554 H,0.2114164509,1.7318496975,-1.4094457233 H,-1.2278550316,3.8420576386,-1.8002727862 H,-2.7378469145,1.4150067467,-0.6832218125 H,-1.6096216256,4.9222596075,0.3854695191 H,-0.0546332565,3.5382083457,1.7908587115 H,-2.9461610558,3.7781284751,-1.4128797983 N,0.7249365673,0.9335390328,1.2434215143 N,-0.5772323435,-0.1659418749,-0.9869033044 C,1.9671179683,1.223865834,1.3075094728 H,2.5843723095,0.4735398523,1.8042137652 C,-0.2190511043,-0.5494941259,-2.1630949361 H,0.213794576,0.2069597033,-2.8241477747 B,0.1252242584,-0.5100495876,1.6603029002 B,-0.8438095769,-1.090371412,0.3525778282 O,-2.2864168257,-0.9749939867,0.5782592351 O,-0.6486760733,-0.2546262447,2.8832321849 O,-0.5145613892,-2.4877624343,0.0700963605 O,1.2565992836,-1.3683157821,2.0078964734 C,-1.9629176441,-0.5809068214,2.9669734986 C,-4.6928160385,-1.1540614673,3.3130505578 C,-2.5566030332,-0.5354981943,4.2303135414 C,-2.7595633435,-0.9288741078,1.8523008301 C,-4.1126983623,-1.2089144443,2.0484662752 213 C,-3.907974405,-0.8165060534,4.412173012 H,-1.9217306211,-0.2658819139,5.0696011441 H,-4.6996959573,-1.4707129868,1.1725539232 H,-4.3390331264,-0.7704034069,5.4072909962 H,-5.7484716564,-1.3761115997,3.4327279982 C,1.6648036107,-2.3100783284,1.1189191021 C,2.5622896265,-4.350647288,-0.5803436577 C,2.9799001226,-2.7685658794,1.1873978087 C,0.7841792578,-2.8756106471,0.17049498 C,1.2485545235,-3.8918894502,-0.6644002436 C,3.4327200894,-3.7834614319,0.3458559574 H,3.635149476,-2.3193314384,1.9286826361 H,0.5495294577,-4.3177724524,-1.3797160913 H,4.4597850184,-4.1268530292,0.4207475668 H,2.898356865,-5.1444811546,-1.240150903 C,2.641636291,2.4267921915,0.7689109798 C,3.940719065,4.6758742777,-0.2319616595 C,2.853468804,2.5532954514,-0.6066820041 C,3.1115889978,3.4063266998,1.6472111246 C,3.7484706411,4.5358259534,1.1417669509 C,3.50266972,3.6805683424,-1.1034414186 H,2.5179777063,1.7686235875,-1.2789388621 H,2.9592940091,3.2907992644,2.7163281956 H,4.0972246284,5.3062130651,1.8221199587 H,3.665881192,3.7801961447,-2.1717991985 H,4.4405859563,5.556735308,-0.6223987096 C,-0.3886431258,-1.8761463875,-2.7563733382 C,-0.7029331763,-4.3256389588,-4.0405932015 C,0.5705827756,-2.313474361,-3.678022678 C,-1.5288544126,-2.6516629481,-2.5103772925 C,-1.6844008961,-3.8712996071,-3.1580268054 C,0.4250875853,-3.5477167795,-4.3009884874 H,1.4354273082,-1.6897577777,-3.8878498825 H,-2.2889589025,-2.2858924437,-1.8272918399 H,-2.5713613487,-4.4695427301,-2.9761862217 H,1.1805475366,-3.8963501618,-4.9974905563 H,-0.8266709753,-5.2822296374,-4.5391149444 IB-Z,E[1,2]MeOH (Intermediate dicoordinate 1,2-B2cat2-Z,E-diimine 1 complex in MeOH) boat_cydiimph2_ZE_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1646192 Zero-point correction= 0.572628 (Hartree/Particle) 214 Thermal correction to Energy= 0.603875 Thermal correction to Enthalpy= 0.604819 Thermal correction to Gibbs Free Energy= 0.508678 Sum of electronic and ZPE= -1696.591991 Sum of electronic and thermal Energies= -1696.560744 Sum of electronic and thermal Enthalpies= -1696.559800 Sum of electronic and thermal Free Energies= -1696.655941 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.937 129.052 202.347 H,-2.4764056813,1.9733951558,-2.0487643278 C,-2.144443033,2.19139699,-1.0284957811 C,-1.3210562619,4.0066553,0.5344028564 C,-0.389436399,1.7041978132,0.691151489 C,-0.057014082,3.1886781289,0.8162170197 C,-0.8664766962,1.39977771,-0.7327705886 C,-1.8863444395,3.6896026152,-0.8520223874 H,-2.074987735,3.7764298887,1.2979147134 H,-1.2080827491,1.4883753647,1.3862187916 H,0.7216351468,3.4733080509,0.0986404444 H,-0.075865557,1.7179478605,-1.4176445109 H,-1.1730304577,4.0202148726,-1.6182081071 H,-2.9293804639,1.849960169,-0.3424369504 H,-1.0944214227,5.0737673034,0.6161003271 H,0.32525552,3.3870347895,1.8224408014 H,-2.815932751,4.2418346466,-1.0191296534 N,0.6916489879,0.7727696136,1.0787051432 N,-1.1006190594,-0.0500303308,-0.907792236 C,1.899820827,1.0269983767,0.7239062579 H,2.0800349705,1.8888087198,0.078441764 C,-1.1424538967,-0.5830425777,-2.0724807634 H,-1.4269970982,-1.6344752418,-2.0969235052 B,-0.0045106708,-0.6219761064,1.5744975995 B,-1.2661624,-0.9574674205,0.4378969442 O,-2.6059245057,-0.6350074728,0.929324026 O,-0.5003744271,-0.3364825671,2.9261932322 O,-1.2386698314,-2.3631099526,0.0063788691 O,0.9768193412,-1.6949936102,1.6534369988 C,-1.8092221596,-0.5192543477,3.2369045249 C,-4.4832183998,-0.8099676181,4.05299881 C,-2.1546002886,-0.5303504041,4.5898781731 C,-2.8324060097,-0.6627723373,2.2717460382 C,-4.1524489381,-0.8064387105,2.7004031894 C,-3.4761876453,-0.6724910969,5.0042181581 215 H,-1.3496444302,-0.4182414999,5.3107086433 H,-4.916421224,-0.9129390698,1.9353937061 H,-3.7114691992,-0.6752719665,6.063848751 H,-5.5195887946,-0.92231145,4.3552030484 C,1.0998991407,-2.5506332504,0.6086749931 C,1.4066819908,-4.4391495521,-1.4402960281 C,2.3401857919,-3.1384899034,0.3617124749 C,-0.0047973279,-2.9053969471,-0.1966992405 C,0.1653979976,-3.8456053577,-1.2112161072 C,2.4976950667,-4.0803958434,-0.6544692072 H,3.17493798,-2.8471839108,0.9948853139 H,-0.7017204247,-4.1089800819,-1.8109607157 H,3.4711597729,-4.5292454718,-0.8256100951 H,1.5148483398,-5.1729214666,-2.2327304963 C,3.0864335846,0.274775467,1.140270351 C,5.4137882598,-1.0553931513,1.8933203122 C,4.1407149718,0.1361062723,0.2299559024 C,3.2145076459,-0.2262111796,2.4418821739 C,4.3808832874,-0.8826113496,2.8161633961 C,5.2933435818,-0.5485981423,0.5996357249 H,4.0445349852,0.5534141784,-0.7689442258 H,2.4073668407,-0.0819140986,3.1535158138 H,4.4861550964,-1.2613760209,3.8276936274 H,6.1011394497,-0.6747890603,-0.1138630265 H,6.3207129703,-1.5742537412,2.1883691617 C,-0.8642310119,0.073596636,-3.3665013418 C,-0.3806681131,1.207393474,-5.8652619272 C,0.3715969515,0.6731204707,-3.6343620834 C,-1.8432891907,0.0127958641,-4.3637199126 C,-1.6058454676,0.5961846258,-5.6044340153 C,0.6098890043,1.2343875181,-4.8848730042 H,1.1504168044,0.6727564391,-2.8767581671 H,-2.7891300162,-0.4808771404,-4.1593242402 H,-2.3735820561,0.5631076656,-6.3706775061 H,1.5724131253,1.6896240158,-5.094464973 H,-0.1928571769,1.6522334243,-6.8374143812 IB-Z,Z[1,2]MeOH (Intermediate dicoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in MeOH) boat_cydiimph2_ZZ_1-2-b2cat2_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1625792 Zero-point correction= 0.573653 (Hartree/Particle) Thermal correction to Energy= 0.604659 Thermal correction to Enthalpy= 0.605603 Thermal correction to Gibbs Free Energy= 0.510652 216 Sum of electronic and ZPE= -1696.588926 Sum of electronic and thermal Energies= -1696.557920 Sum of electronic and thermal Enthalpies= -1696.556976 Sum of electronic and thermal Free Energies= -1696.651928 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.429 128.591 199.842 H,-0.9035642668,-1.6250572535,-3.0388388074 C,-0.6043937748,-2.0877336214,-2.0934305326 C,-1.1566725311,-3.8826077926,-0.3862030247 C,-0.1640697047,-1.7324696078,0.3277480096 C,-1.1505652309,-2.8285240592,0.7289741437 C,-0.6569371282,-1.054629299,-0.9631487595 C,-1.5196173357,-3.2644649294,-1.740770051 H,-0.1628729752,-4.3435970423,-0.4515405303 H,0.7844474366,-2.2328321787,0.1029049224 H,-2.1604488402,-2.4252954283,0.8515183335 H,-1.6954310248,-0.7544003792,-0.7913680213 H,-2.5585302971,-2.9089305944,-1.7089739948 H,0.4318634043,-2.4251171032,-2.2117683929 H,-1.8651568259,-4.6771117764,-0.1339966496 H,-0.8437199899,-3.2678350283,1.6835497626 H,-1.4635178556,-4.0216448877,-2.5284558877 N,0.215774613,-0.7113633163,1.3204315563 N,0.1253960199,0.1547725164,-1.2616473772 C,-0.5452565718,-0.14743898,2.178171767 H,-0.053201043,0.5879884152,2.8167136144 C,-0.4247906367,1.2166796169,-1.7346701034 H,0.2554541956,2.0539450513,-1.8759415116 B,1.7068590896,-0.1753468376,0.9572021224 B,1.676201133,0.1880817148,-0.7269604942 O,2.3742189245,-0.7842419045,-1.5654261744 O,2.6180936203,-1.2667931772,1.3131765228 O,2.200679472,1.5301938126,-1.004421956 O,1.9914011592,0.9684321493,1.8199438307 C,3.4290637974,-1.8286875807,0.3799634501 C,5.1560239161,-3.1356749641,-1.4123632166 C,4.4159174342,-2.7057459822,0.8353466061 C,3.3107589747,-1.5990774391,-1.0104434126 C,4.1794372462,-2.2609079165,-1.8803356394 C,5.2764491156,-3.3578136129,-0.0433382916 H,4.4847839738,-2.863532321,1.9079792263 H,4.0633180525,-2.0662133408,-2.9428393693 H,6.0322038645,-4.0336672515,0.3441532633 217 H,5.8158186349,-3.6343050986,-2.1152573141 C,1.8715860518,2.2215576422,1.3093852511 C,1.7051556929,4.8704261282,0.3931329008 C,1.6708848154,3.2779402222,2.1985201245 C,1.989019082,2.4999780353,-0.0711075572 C,1.898791288,3.8229833435,-0.5056752506 C,1.58894289,4.5952804318,1.7524907583 H,1.5900105675,3.0375445368,3.2550025314 H,1.9958929747,4.0094095968,-1.5720203598 H,1.435478086,5.3974751592,2.4673295922 H,1.6446717311,5.8905188717,0.0275053782 C,-2.0018712098,-0.3574076026,2.3444325472 C,-4.743781667,-0.7395469552,2.6332779318 C,-2.4900919356,-1.087478979,3.4302456625 C,-2.8857411597,0.2161391367,1.4254481887 C,-4.2565879371,0.0194032872,1.5708838115 C,-3.861240051,-1.2857065212,3.5644740587 H,-1.7977422226,-1.5143681214,4.1498084545 H,-2.5013252587,0.8197153147,0.6066427156 H,-4.9406336206,0.4608195365,0.8526837881 H,-4.2407287795,-1.8680090157,4.3980480268 H,-5.8121493217,-0.8974539508,2.7420335123 C,-1.8339429613,1.5186038014,-2.0218958059 C,-4.4756048026,2.3670116433,-2.3726866047 C,-2.1899521535,2.8592469425,-1.7998194962 C,-2.8131405098,0.6145232347,-2.4625887805 C,-4.1238654528,1.0441265216,-2.6384707188 C,-3.5058936314,3.2768214763,-1.9556783703 H,-1.4262907639,3.5651040536,-1.4829384292 H,-2.5599575841,-0.410994186,-2.7027910583 H,-4.8729740371,0.3416937034,-2.9888691078 H,-3.7716524593,4.310711862,-1.76172894 H,-5.503075726,2.6910223381,-2.5056213936 IB-E,E[1,1]DMF (Intermediate dicoordinate 1,1-B2cat2-E,E-diimine 1 complex in DMF) boat_cydiimph2_EE_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1481842 Zero-point correction= 0.571932 (Hartree/Particle) Thermal correction to Energy= 0.603457 Thermal correction to Enthalpy= 0.604401 Thermal correction to Gibbs Free Energy= 0.509201 Sum of electronic and ZPE= -1696.576253 Sum of electronic and thermal Energies= -1696.544727 218 Sum of electronic and thermal Enthalpies= -1696.543783 Sum of electronic and thermal Free Energies= -1696.638984 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.675 129.734 200.367 H,3.1516077004,2.7580833848,1.3565894505 C,2.3437818835,3.0736632954,0.6880926538 C,0.8110291143,4.9825956567,0.059173354 C,-0.0461327434,2.6416324668,0.0414927522 C,-0.4021756919,4.09426834,0.3502835333 C,1.1104168443,2.2068136941,0.9601438083 C,2.0148947675,4.5528107251,0.8996346175 H,1.0627166251,4.9129524012,-1.0066235398 H,0.2978618504,2.5897126785,-0.9956203556 H,-0.6761012263,4.2100106959,1.4058758873 H,0.777825736,2.3650278943,1.9941564723 H,1.7919981535,4.7241900959,1.9606656234 H,2.6706772705,2.8950390524,-0.3421769095 H,0.5581033236,6.0269278527,0.2642127884 H,-1.2642179621,4.3933139227,-0.25516626 H,2.8898537293,5.1613530322,0.6523412136 N,-1.1613111772,1.6718413105,0.1106454965 N,1.4178781845,0.7619020233,0.8142553975 C,-2.1750165754,1.9137287452,0.8528800176 H,-2.1675772899,2.7988350196,1.4908687092 C,1.9831808453,0.2063927296,1.8209101249 H,2.250900728,0.854281619,2.661385922 B,-0.7757871957,0.2054129197,-0.6396697667 B,0.9539963493,0.14554754,-0.6830233655 O,1.7294544979,1.0045220309,-1.6299965108 O,1.5504506533,-1.1866944314,-0.833033633 O,-1.4989863904,0.0939238194,-1.9261483753 O,-1.3464433125,-0.8656303403,0.220168813 C,2.76930707,-0.9902633291,-1.3848706204 C,5.0856071141,-0.148020543,-2.6339742255 C,3.8109186469,-1.8899119037,-1.5060994031 C,2.8753273909,0.3250190884,-1.8710770285 C,4.0236575174,0.7655072009,-2.5011791096 C,4.982747308,-1.4457525022,-2.1454335148 H,3.7194780293,-2.8996992905,-1.1178417735 H,4.0974038275,1.7809251917,-2.8778910317 H,5.8188259913,-2.1295558328,-2.2546000825 H,6.000917592,0.1717989656,-3.1223651321 C,-2.2744478946,-1.5098312023,-0.5194253291 219 C,-4.0826877545,-2.4961109871,-2.3620578399 C,-3.0813559636,-2.5652521493,-0.1435554861 C,-2.3615815364,-0.938859976,-1.8027984599 C,-3.2574174307,-1.4191241722,-2.7384473254 C,-3.9986642978,-3.0556645148,-1.0925346772 H,-3.0133987415,-2.9871510615,0.854339834 H,-3.3247743094,-0.9697366137,-3.7241002516 H,-4.6457911199,-3.8855000362,-0.8254516213 H,-4.7948961522,-2.8928066055,-3.0791497035 C,-3.4070070857,1.1030763189,0.8713968143 C,-5.8164586273,-0.2923374349,0.9126980741 C,-3.8820840201,0.5699126034,2.0737983354 C,-4.1501084652,0.9580288322,-0.3029497765 C,-5.363002723,0.2724624649,-0.2759555279 C,-5.0719124993,-0.1490797046,2.0856583279 H,-3.3107281148,0.7044860058,2.9876478387 H,-3.7795755092,1.3927916948,-1.2261376463 H,-5.9422195578,0.1684686066,-1.1880966099 H,-5.4284162446,-0.5860837157,3.0128720971 H,-6.7532846783,-0.8405117317,0.9304493485 C,2.3105864059,-1.2170931336,2.0044534986 C,2.9871713706,-3.868346227,2.5212891104 C,1.4019280572,-2.2381397733,1.7017094498 C,3.5378463729,-1.5246555106,2.6022127956 C,3.8854537592,-2.8512452575,2.8381065978 C,1.7434860473,-3.5589937778,1.9683718375 H,0.4387764345,-1.9859210312,1.2685938674 H,4.2215443965,-0.7228155684,2.8676672888 H,4.8474681874,-3.0883394022,3.2805775259 H,1.0379599916,-4.3524340903,1.7429405085 H,3.249338523,-4.9033190686,2.7182841068 IB-E,Z[1,1]DMF (Intermediate dicoordinate 1,1-B2cat2-E,Z-diimine 1 complex in DMF) boat_cydiimph2_EZ_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1438619 Zero-point correction= 0.572080 (Hartree/Particle) Thermal correction to Energy= 0.603742 Thermal correction to Enthalpy= 0.604686 Thermal correction to Gibbs Free Energy= 0.507984 Sum of electronic and ZPE= -1696.571782 Sum of electronic and thermal Energies= -1696.540120 Sum of electronic and thermal Enthalpies= -1696.539175 Sum of electronic and thermal Free Energies= -1696.635878 220 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.854 129.518 203.527 H,1.1656256939,-3.3441177094,1.5188356728 C,0.4162166187,-2.6538752268,1.9207213967 C,-1.8294235468,-2.4877833669,3.0909402491 C,-1.2498532871,-0.8749471433,1.3052669645 C,-2.3963397962,-1.6776397852,1.9180038787 C,-0.1730738049,-1.8381536418,0.7693971328 C,-0.7068160172,-3.4217319791,2.6268635747 H,-1.4423478344,-1.801022427,3.8545073612 H,-0.8008051613,-0.2864506145,2.113332172 H,-2.8331716828,-2.3652934398,1.1881270767 H,-0.6706722266,-2.5270036264,0.0762701101 H,-1.1239159101,-4.1660945113,1.9360600969 H,0.9169212289,-1.9770120161,2.619156696 H,-2.6326016006,-3.0673879456,3.5554859148 H,-3.1845829317,-0.9957553046,2.2530096716 H,-0.2941536281,-3.9703594239,3.4787975885 N,-1.5406768699,0.1308645335,0.2676555329 N,0.8363876218,-1.0826858603,-0.0122220133 C,-2.4304420124,0.0709183044,-0.6437398972 H,-2.4543265268,0.9259180687,-1.3214065684 C,1.3238749951,-1.6844768702,-1.0330719795 H,1.0532699392,-2.7357404801,-1.1712289169 B,-0.3802185069,1.3451729946,0.3269844733 B,1.1141209102,0.4953092157,0.5735567606 O,1.4917689297,0.2310203925,1.9908882034 O,2.3466424267,0.9832083561,-0.0495697391 O,-0.816638039,2.2295807028,1.4346463834 O,-0.5558845903,2.1407409919,-0.9039805036 C,3.3559601995,0.5858844292,0.760014673 C,5.0636647514,-0.2910558005,2.7459898993 C,4.7136266059,0.5962185908,0.5052547463 C,2.842433647,0.1377247428,1.9897139427 C,3.6794545186,-0.302576976,2.997528298 C,5.5696390333,0.1469066129,1.5270028068 H,5.095861896,0.9381057862,-0.4516237098 H,3.2777283449,-0.6428462022,3.9468402987 H,6.6416616327,0.1405743035,1.3560469928 H,5.7446179693,-0.6347842466,3.5184565333 C,-1.2788075051,3.2333980264,-0.5464794516 C,-2.6756374554,5.3073455838,0.6275712712 C,-1.8070570144,4.2125367846,-1.3650234952 C,-1.439387375,3.276396819,0.8500617869 221 C,-2.1359825756,4.3065318043,1.4549648193 C,-2.5153776763,5.2621570058,-0.7526197447 H,-1.6745646435,4.1674164645,-2.4412867904 H,-2.2560030523,4.3354982743,2.533147927 H,-2.9418003586,6.0457412763,-1.371062042 H,-3.2265746282,6.1267011047,1.0788849432 C,-3.3856199359,-1.0345071716,-0.8974010634 C,-5.1727695455,-3.1113558312,-1.3877052757 C,-4.7270572516,-0.8967063816,-0.5338152828 C,-2.9444028976,-2.1950058283,-1.5386778043 C,-3.8411215984,-3.2328750189,-1.7801091341 C,-5.6149241486,-1.9423874131,-0.7698673257 H,-5.0651510812,0.0151791872,-0.050715613 H,-1.9063168243,-2.2799534478,-1.8484640954 H,-3.4980452251,-4.1358460527,-2.2747949806 H,-6.653671303,-1.8431843359,-0.4715853363 H,-5.8683218019,-3.9240889717,-1.5710880561 C,2.1756915363,-1.1123636983,-2.086627791 C,3.7301149527,-0.1799905737,-4.2002248321 C,1.9183426084,0.1494046309,-2.6372668277 C,3.1861054749,-1.9176171307,-2.6228431291 C,3.9788184823,-1.4412360286,-3.6626519972 C,2.6923871084,0.6063359445,-3.6967363426 H,1.1121893946,0.7591987367,-2.2392174954 H,3.3544027781,-2.9102635204,-2.214194489 H,4.7770583348,-2.0584688621,-4.0616580514 H,2.4887109553,1.5796845088,-4.1314133038 H,4.3363932821,0.1872776871,-5.0225447707 IB-Z,E[1,1]DMF (Intermediate dicoordinate 1,1-B2cat2-Z,E-diimine 1 complex in DMF) boat_cydiimph2_ZE_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1496584 Zero-point correction= 0.572055 (Hartree/Particle) Thermal correction to Energy= 0.603585 Thermal correction to Enthalpy= 0.604529 Thermal correction to Gibbs Free Energy= 0.508156 Sum of electronic and ZPE= -1696.577603 Sum of electronic and thermal Energies= -1696.546073 Sum of electronic and thermal Enthalpies= -1696.545129 Sum of electronic and thermal Free Energies= -1696.641502 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K 222 Total 378.755 129.510 202.834 H,-2.8979781815,1.615475118,-2.0164573544 C,-2.6302637018,1.8582746224,-0.9826096413 C,-2.2461248915,3.7330389746,0.669979584 C,-0.7842844433,1.7169047094,0.7224592849 C,-0.8160524257,3.2328384673,0.8979299642 C,-1.1998330432,1.3733731811,-0.7195813617 C,-2.7377854851,3.3629933276,-0.7308839811 H,-2.9090812879,3.2871272128,1.4221221973 H,-1.5156084583,1.2774248458,1.4079761588 H,-0.1538837161,3.7210263865,0.1722196166 H,-0.5118806395,1.895386212,-1.3906069697 H,-2.1335871964,3.8955164926,-1.4765951685 H,-3.3073262596,1.3047878326,-0.3212522689 H,-2.2814434681,4.8173348052,0.8100133211 H,-0.4632815129,3.4913290797,1.9017579137 H,-3.7747209698,3.6836597209,-0.868454029 N,0.4905450151,1.0446332477,1.0544028561 N,-1.1176392093,-0.0773515934,-0.9609715952 C,1.5916546823,1.6923094004,0.9848100906 H,1.5784815694,2.7212811228,0.6222802392 C,-0.8847847979,-0.5707801136,-2.1176545717 H,-0.9246018947,-1.659043753,-2.1738444742 B,0.3068351039,-0.6325551069,1.205403726 B,-1.1800746007,-1.0249082348,0.3969166893 O,-2.4907369412,-0.7244194272,1.0384016548 O,-1.2978386867,-2.4190514003,-0.0770247339 O,0.4272714024,-1.0268800857,2.6263212396 O,1.4832064247,-1.232973802,0.5305311997 C,-2.6184357524,-2.7205590399,-0.0268593821 C,-5.3521067282,-2.9370013868,0.3291901942 C,-3.256363653,-3.8462443413,-0.5118422311 C,-3.3306662373,-1.7057782824,0.636530801 C,-4.6975437353,-1.7943212001,0.8229803442 C,-4.6468871275,-3.9416836682,-0.3235809512 H,-2.6969372683,-4.6253368884,-1.0198535672 H,-5.2394173755,-1.0062942174,1.3363184824 H,-5.1736679125,-4.8142598071,-0.697187196 H,-6.4255328107,-3.0312723165,0.4612628097 C,2.1683113183,-1.9121757651,1.4719145039 C,3.2557856852,-3.1258810522,3.706982317 C,3.3429827219,-2.6236014417,1.3255025009 C,1.5350913273,-1.7947962786,2.7240891187 C,2.0596447349,-2.3966750197,3.8512479697 C,3.884828328,-3.2348611133,2.4725511695 223 H,3.8314035518,-2.6939310068,0.3586827795 H,1.5681456155,-2.2963143197,4.8137659824 H,4.8073281034,-3.800898535,2.3859489914 H,3.689703842,-3.6090282617,4.5771142728 C,2.9024639651,1.1630257543,1.4076016626 C,5.4133356643,0.297243713,2.2469426974 C,3.9699679026,1.1402930969,0.5039740965 C,3.0987026894,0.7738963917,2.7348301371 C,4.3602100473,0.3562033504,3.1554590535 C,5.2153516817,0.682551836,0.9193468402 H,3.8165538156,1.463613612,-0.5217329299 H,2.2666268204,0.8109515086,3.4312113813 H,4.5118911727,0.0631597673,4.1895785069 H,6.037286769,0.639913058,0.2119658936 H,6.3917517452,-0.0430769466,2.5714946884 C,-0.5683406654,0.1763237045,-3.3548274245 C,0.03594276,1.4877730988,-5.7384515377 C,0.5712914999,0.9841576709,-3.4393437556 C,-1.3884536727,0.0052865452,-4.4742643486 C,-1.0927626964,0.6741406664,-5.6586112102 C,0.871513087,1.6343524883,-4.6321944698 H,1.2277768195,1.0820094877,-2.5787093891 H,-2.2576653546,-0.6429879625,-4.410727704 H,-1.7392666634,0.5519550448,-6.5215595237 H,1.7605235736,2.2531081601,-4.6983147998 H,0.2704500248,2.0002686739,-6.6660163808 IB-Z,Z[1,1]DMF (Intermediate dicoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in DMF) boat_cydiimph2_ZZ_b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1456299 Zero-point correction= 0.572661 (Hartree/Particle) Thermal correction to Energy= 0.604183 Thermal correction to Enthalpy= 0.605127 Thermal correction to Gibbs Free Energy= 0.508523 Sum of electronic and ZPE= -1696.572969 Sum of electronic and thermal Energies= -1696.541447 Sum of electronic and thermal Enthalpies= -1696.540503 Sum of electronic and thermal Free Energies= -1696.637107 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.131 129.238 203.321 H,2.4980266462,1.9456870717,-1.6400926021 224 C,1.6458703997,1.3721173137,-2.0201730323 C,-0.3166873959,1.3907334837,-3.6232020424 C,-0.5623690949,0.3572184922,-1.3852227929 C,-1.2857361835,1.1688726611,-2.4561637567 C,0.6702399908,1.1172669073,-0.8656822248 C,0.9416964993,2.1251023256,-3.1518963811 H,-0.0359581158,0.4225444726,-4.0569901422 H,-0.1971851223,-0.5524998249,-1.8784894277 H,-1.604416601,2.1421719853,-2.0775166796 H,0.3384686639,2.0764596376,-0.4616104878 H,0.6617968577,3.126211949,-2.7986924667 H,2.0205445277,0.4054626317,-2.3746539462 H,-0.8167170563,1.9647004378,-4.4088384437 H,-2.1798031431,0.625676016,-2.7790008606 H,1.6378098453,2.2615676027,-3.984905547 N,-1.3198218367,-0.1673545688,-0.2392031502 N,1.3288197062,0.345100888,0.2065885658 C,-2.3528231347,0.3067502441,0.3458322806 H,-2.7332491594,-0.3263318225,1.1491562351 C,1.9976543171,0.914886864,1.1343900474 H,2.4955850615,0.2429962186,1.8339503061 B,-0.5989143971,-1.6038028925,0.2566880161 B,1.1153435909,-1.3209448309,0.1653911971 O,1.7607055841,-1.7261993917,-1.114944562 O,1.9902859885,-1.8572085237,1.222728933 O,-1.1078876205,-2.6095248,-0.7149066838 O,-1.2184986274,-1.9607230067,1.5458981311 C,3.1572817352,-2.1821526813,0.61000375 C,5.2909546244,-2.7815083131,-1.0418961135 C,4.3492852008,-2.5673630069,1.1927388551 C,3.0186840128,-2.0967035047,-0.7867508289 C,4.0748166052,-2.3904771204,-1.6294881659 C,5.425750385,-2.8687615484,0.3392252449 H,4.4444804942,-2.6318882908,2.2720009169 H,3.9599286484,-2.3220860708,-2.7066397659 H,6.3749495412,-3.1718420242,0.7699471585 H,6.136436222,-3.0167864245,-1.6809578865 C,-2.1722674463,-2.883909804,1.267303748 C,-3.9322709413,-4.7637362186,0.2641763966 C,-3.1038788618,-3.4337831344,2.1267490776 C,-2.1098970346,-3.2603122831,-0.0867094296 C,-2.982806954,-4.1988116461,-0.6061443215 C,-3.9920591452,-4.390052011,1.6017929893 H,-3.1415918376,-3.1348142641,3.1694229944 H,-2.9290694828,-4.4862243307,-1.6512773895 H,-4.7341580846,-4.8389696607,2.2546183816 225 H,-4.6283622264,-5.5031005442,-0.1198231891 C,-3.1251659159,1.5452011608,0.1207073222 C,-4.7429828853,3.8027659359,-0.1612224316 C,-4.5198827907,1.4170584917,0.102165946 C,-2.5477619454,2.8168862144,0.0391907189 C,-3.3574566787,3.9401937883,-0.0970691054 C,-5.3238737281,2.539524989,-0.0627007715 H,-4.9673032757,0.4325079884,0.2062373723 H,-1.4708462252,2.9336320144,0.0997999102 H,-2.9034947208,4.9243402923,-0.1508280125 H,-6.4027182145,2.4295121874,-0.0988966326 H,-5.3700928608,4.6814381167,-0.2739493883 C,2.1430395093,2.3743127489,1.3423720284 C,2.453940661,5.1057471272,1.7910948338 C,1.0378639085,3.1539048475,1.6989924916 C,3.4081351156,2.9580300368,1.2362870593 C,3.5572338163,4.3261402974,1.4488839016 C,1.1966779898,4.5179582557,1.9234661109 H,0.0637821942,2.6857516602,1.813720273 H,4.2662902199,2.3436470524,0.9796223464 H,4.5377053153,4.7811983715,1.3530683984 H,0.3381158419,5.1199583251,2.2035539048 H,2.5750590245,6.1705994394,1.9627218189 IB-E,E[1,2]DMF (Intermediate dicoordinate 1,2-B2cat2-E,E-diimine 1 complex in DMF) boat_cydiimph2_EE_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1614746 Zero-point correction= 0.572521 (Hartree/Particle) Thermal correction to Energy= 0.603611 Thermal correction to Enthalpy= 0.604555 Thermal correction to Gibbs Free Energy= 0.510016 Sum of electronic and ZPE= -1696.588953 Sum of electronic and thermal Energies= -1696.557863 Sum of electronic and thermal Enthalpies= -1696.556919 Sum of electronic and thermal Free Energies= -1696.651459 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.772 129.096 198.975 H,-2.5160804997,2.1619130393,-2.3916830264 C,-2.2935335807,2.4115871385,-1.3493489756 C,-1.9179372466,4.3052989612,0.2837150339 226 C,-0.591166016,2.2018712008,0.4661285697 C,-0.5453932322,3.7209489783,0.6245781536 C,-0.9219817462,1.8328520032,-0.9799835184 C,-2.3259596187,3.9264572665,-1.1404885534 H,-2.6609919168,3.9202156992,0.9935134441 H,-1.3931936223,1.8218559899,1.1088191061 H,0.2030947729,4.157680729,-0.0471607981 H,-0.1502263458,2.2700409182,-1.6285788382 H,-1.6357840885,4.4001810628,-1.8505298065 H,-3.0480905688,1.918864061,-0.7230778059 H,-1.894791861,5.3930542001,0.3970770808 H,-0.2547903704,3.9623899319,1.6518226063 H,-3.3278333538,4.3041290561,-1.3654982397 N,0.6177532507,1.4862524998,0.9158897962 N,-0.9295119138,0.3653427613,-1.2043509057 C,1.7783444664,1.9792117263,0.6701997185 H,1.8402393704,2.8777379546,0.0541741909 C,-0.7963232437,0.0154635413,-2.4371872682 H,-0.4991001898,0.7938722103,-3.1459387047 B,0.168408721,-0.017756458,1.3447321005 B,-0.9435904293,-0.5984042031,0.1286089547 O,-2.3396976586,-0.5760137804,0.564015142 O,-0.4705208612,0.1501332291,2.6539873537 O,-0.5705841939,-1.9601793623,-0.257947357 O,1.3377111995,-0.8702847639,1.4873463584 C,-1.6847857211,-0.3860917912,2.9019986727 C,-4.2200652845,-1.4009484724,3.5804541627 C,-2.0640989997,-0.5556967311,4.2355405038 C,-2.6032245598,-0.7407832376,1.8831866047 C,-3.8535293619,-1.2437325275,2.2448839513 C,-3.3177642538,-1.0558468265,4.5822167138 H,-1.3425810179,-0.2750476297,4.997398029 H,-4.5367734368,-1.5045943564,1.4416929608 H,-3.5811216974,-1.1724684437,5.6288713119 H,-5.2013465697,-1.7927561961,3.8290366208 C,1.709694255,-1.6528278392,0.4530209232 C,2.518605342,-3.4157691899,-1.5696108799 C,3.0587583652,-1.9584320502,0.2743310335 C,0.7479752215,-2.2240137086,-0.4116494877 C,1.1671263154,-3.1048597144,-1.4084379669 C,3.4664344639,-2.8358581466,-0.7316248482 H,3.776608745,-1.5032851194,0.9523852702 H,0.4082006146,-3.5457912433,-2.0497178338 H,4.5209574945,-3.0646143627,-0.8516764885 H,2.8224107387,-4.1055454914,-2.351009644 C,3.0530510978,1.4644390685,1.178692745 227 C,5.5325550718,0.6159465221,2.1227949162 C,3.1647612973,0.9319247662,2.4692959611 C,4.1933029297,1.5997756014,0.3776533926 C,5.4269372164,1.1544536978,0.8405945572 C,4.4051752045,0.5180897308,2.9398797529 H,2.2814728353,0.8604184005,3.0951548138 H,4.1035888463,2.0412828529,-0.6112383357 H,6.3058297128,1.2405720283,0.210133176 H,4.4949427534,0.1164993694,3.9440494791 H,6.4981792315,0.2849067787,2.4924904409 C,-1.0669013193,-1.2936178338,-3.027854394 C,-1.5825302884,-3.7185081473,-4.293776218 C,-0.3586649433,-1.6479998301,-4.1834387485 C,-2.0677482053,-2.1400595085,-2.5322125339 C,-2.3242927034,-3.3471017782,-3.1709014957 C,-0.6002131755,-2.8687334242,-4.8025193659 H,0.391695235,-0.9692231554,-4.5799682708 H,-2.6378186748,-1.8390780864,-1.6595257398 H,-3.1038802739,-4.0016656636,-2.7948626695 H,-0.0355672023,-3.1518845021,-5.6846693255 H,-1.7838245418,-4.6661893698,-4.7838955383 IB-E,Z[1,2]DMF (Intermediate dicoordinate 1,2-B2cat2-E,Z-diimine 1 complex in DMF) boat_cydiimph2_EZ_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.156283 Zero-point correction= 0.572719 (Hartree/Particle) Thermal correction to Energy= 0.603927 Thermal correction to Enthalpy= 0.604871 Thermal correction to Gibbs Free Energy= 0.509409 Sum of electronic and ZPE= -1696.583564 Sum of electronic and thermal Energies= -1696.552356 Sum of electronic and thermal Enthalpies= -1696.551412 Sum of electronic and thermal Free Energies= -1696.646874 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.970 129.069 200.918 H,-2.0972077208,1.5815627093,-2.2960108402 C,-1.9417161631,1.8597035218,-1.2485626571 C,-1.6468955275,3.8091596643,0.3474026902 C,-0.3608054053,1.7180086298,0.6736002732 C,-0.291501294,3.2411484191,0.7806855116 C,-0.5918661189,1.3000003608,-0.7837055074 228 C,-1.981177079,3.3813508863,-1.0835060179 H,-2.4271939008,3.4501608257,1.0306084762 H,-1.2393744242,1.4029208873,1.2488937292 H,0.491977045,3.6476883801,0.1343335324 H,0.2073464728,1.736114677,-1.3958773968 H,-1.2538059947,3.8325754854,-1.7707693391 H,-2.7322571364,1.3826003073,-0.656413575 H,-1.6287226269,4.9004398275,0.421054276 H,-0.0558613857,3.5210009481,1.8124766548 H,-2.9688593275,3.7530848178,-1.3723371504 N,0.7294151384,0.9202087601,1.2526547529 N,-0.5634850146,-0.1709365409,-0.9811405718 C,1.971599474,1.2103433156,1.3071726106 H,2.5904374269,0.4575262536,1.7981898319 C,-0.2026702472,-0.5474770486,-2.1582486145 H,0.2281699227,0.2121711022,-2.8169831417 B,0.1303912753,-0.5295430233,1.6734099671 B,-0.8345819041,-1.1063415466,0.3574301948 O,-2.2747500947,-0.9827119846,0.5703592145 O,-0.6504711562,-0.2713418865,2.8861784373 O,-0.4944196651,-2.495158762,0.0632980835 O,1.2690433492,-1.3765487736,2.0127223416 C,-1.9643566742,-0.5725769492,2.9563318937 C,-4.7123581899,-1.095189258,3.2780157078 C,-2.5748300026,-0.5072610133,4.2119584694 C,-2.7575531554,-0.9172222716,1.8334438101 C,-4.1181312547,-1.1698629146,2.0202381584 C,-3.9333668036,-0.7630344795,4.3826884422 H,-1.9447515033,-0.2414991015,5.055870654 H,-4.7000114308,-1.4274389795,1.1398519442 H,-4.3736938742,-0.7010835501,5.3729784987 H,-5.773229285,-1.2972249588,3.3873556519 C,1.6769464313,-2.31238823,1.1267874921 C,2.58707416,-4.3485388744,-0.5784633225 C,2.9921497256,-2.7734046163,1.1978543463 C,0.8000382827,-2.876853244,0.1697317824 C,1.2732181223,-3.8890422846,-0.666573797 C,3.4516640488,-3.7851006152,0.3551736226 H,3.6432783448,-2.3264447003,1.9440762117 H,0.5780984625,-4.3103142486,-1.38827415 H,4.4786368119,-4.1278698076,0.4349052736 H,2.9270336907,-5.138974845,-1.2404236719 C,2.641730084,2.4139480339,0.7621403592 C,3.9285867439,4.6658242813,-0.2519684503 C,2.8463070872,2.5384825364,-0.6150241561 C,3.1130221751,3.398236663,1.6345468216 229 C,3.7440806682,4.5284231715,1.1230523042 C,3.4887953077,3.6668036171,-1.1183320585 H,2.5099848056,1.7513839128,-1.2840111817 H,2.9668344482,3.2858979281,2.7047475656 H,4.093941767,5.3014645593,1.7996822582 H,3.645569177,3.7642363019,-2.1877560043 H,4.4235068292,5.5471784107,-0.6472928307 C,-0.3749634551,-1.8720382197,-2.7556349317 C,-0.7069653333,-4.3135671708,-4.0508205804 C,0.5595973938,-2.293556615,-3.709528267 C,-1.4993050391,-2.6609490552,-2.4795226766 C,-1.6644201788,-3.8756403615,-3.1342524115 C,0.406276416,-3.5238666807,-4.3385402543 H,1.4113525472,-1.6597509187,-3.9412695582 H,-2.2355325286,-2.3085694796,-1.7645699697 H,-2.5397623664,-4.4839679471,-2.930823772 H,1.1426912911,-3.8597683758,-5.061040082 H,-0.8379416944,-5.2665898628,-4.5542248673 IB-Z,E[1,2]DMF (Intermediate dicoordinate 1,2-B2cat2-Z,E-diimine 1 complex in DMF) boat_cydiimph2_ZE_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.160457 Zero-point correction= 0.572560 (Hartree/Particle) Thermal correction to Energy= 0.603839 Thermal correction to Enthalpy= 0.604783 Thermal correction to Gibbs Free Energy= 0.508755 Sum of electronic and ZPE= -1696.587897 Sum of electronic and thermal Energies= -1696.556618 Sum of electronic and thermal Enthalpies= -1696.555674 Sum of electronic and thermal Free Energies= -1696.651702 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.914 129.143 202.107 H,-2.4970510271,1.9346041501,-2.015495093 C,-2.1642472913,2.1426154471,-0.9934075348 C,-1.3587583479,3.9480967149,0.5918604632 C,-0.3960836561,1.6576825847,0.7122140996 C,-0.0816122497,3.1443283776,0.8561412259 C,-0.872899814,1.3670980842,-0.7151155136 C,-1.9276945114,3.6418383607,-0.7957657246 H,-2.1048757129,3.6958787316,1.3561151833 230 H,-1.2124078192,1.423097983,1.4037061255 H,0.6895780606,3.4486067958,0.1384705827 H,-0.0897861905,1.7095471342,-1.3971050124 H,-1.2234183182,3.9939378561,-1.5606431258 H,-2.9385914575,1.7759388244,-0.3086446337 H,-1.1479229266,5.0172675257,0.6869383784 H,0.3029827901,3.3347314491,1.8629693455 H,-2.8658965957,4.1832309874,-0.9494985417 N,0.6929047942,0.7323047568,1.0868596863 N,-1.0828755735,-0.0820421666,-0.9080593536 C,1.8971351226,0.9967256342,0.727026168 H,2.0698695547,1.8627711383,0.0850258152 C,-1.1111490108,-0.604154582,-2.0771561645 H,-1.3743825998,-1.6610940775,-2.1080929579 B,0.0024639932,-0.6759372748,1.5811658345 B,-1.2545632844,-1.0085838859,0.4352221246 O,-2.5931388535,-0.6840007943,0.9145073388 O,-0.4954481497,-0.3968415212,2.9277432488 O,-1.2101961737,-2.4023739505,-0.0197844931 O,0.9960794786,-1.7332038641,1.6460750845 C,-1.8093912005,-0.4984029947,3.2217609246 C,-4.5080883021,-0.6250827184,4.0149425239 C,-2.1753819281,-0.4320711649,4.5690116872 C,-2.8296733008,-0.6371294569,2.2471351767 C,-4.1598553298,-0.6967636348,2.6681175534 C,-3.5068588845,-0.493391448,4.9729371916 H,-1.3743444269,-0.3255978328,5.2948376666 H,-4.918755903,-0.8005369408,1.8979013834 H,-3.7535442834,-0.4375712005,6.0285845757 H,-5.5524157197,-0.6742246557,4.3067334836 C,1.1259367585,-2.5742055275,0.5976340233 C,1.4556055352,-4.4447364391,-1.4692384702 C,2.371349052,-3.1511428335,0.3462186107 C,0.0238357582,-2.9306560774,-0.2161961475 C,0.2090019238,-3.8621383174,-1.2376109535 C,2.5413480585,-4.0832907377,-0.6776681715 H,3.2008245308,-2.855823942,0.9840389756 H,-0.6536003083,-4.1273649539,-1.843117576 H,3.5195170848,-4.521476455,-0.8500051097 H,1.5714022651,-5.1704770966,-2.2680442571 C,3.0908740194,0.2500428601,1.1342172355 C,5.4350083739,-1.0569517313,1.8793285114 C,4.1581814037,0.1544566443,0.2332291501 C,3.2130891093,-0.286191843,2.4222264826 C,4.3879846643,-0.9292136294,2.793372988 C,5.3194065013,-0.5184799794,0.5978833237 231 H,4.0663581799,0.5968534315,-0.7551691163 H,2.3925283749,-0.1803020119,3.124093883 H,4.488726613,-1.3336596431,3.7953706399 H,6.1374678504,-0.6099951279,-0.1090306193 H,6.348530331,-1.5656633629,2.1714833267 C,-0.8504385112,0.069209291,-3.367368169 C,-0.4097077694,1.235196218,-5.8610478972 C,0.3649536944,0.7092211772,-3.6354248205 C,-1.8296997701,-0.0140086105,-4.3631729999 C,-1.6143923053,0.5843757142,-5.6008490563 C,0.581961464,1.2863813381,-4.8827267221 H,1.146112456,0.7288189303,-2.8807986085 H,-2.7592899888,-0.5380730559,-4.1601568929 H,-2.3830663884,0.5323348006,-6.3649868799 H,1.5289239326,1.7734180511,-5.0912540113 H,-0.2384379052,1.6922445177,-6.8304653344 IB-Z,Z[1,2]DMF (Intermediate dicoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in DMF) boat_cydiimph2_ZZ_1-2-b2cat2_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1591111 Zero-point correction= 0.573555 (Hartree/Particle) Thermal correction to Energy= 0.604638 Thermal correction to Enthalpy= 0.605582 Thermal correction to Gibbs Free Energy= 0.509999 Sum of electronic and ZPE= -1696.585557 Sum of electronic and thermal Energies= -1696.554473 Sum of electronic and thermal Enthalpies= -1696.553529 Sum of electronic and thermal Free Energies= -1696.649112 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.416 128.677 201.172 H,-0.8751389861,-1.5948205545,-3.04351464 C,-0.5685527558,-2.0566360332,-2.0999840854 C,-1.09407612,-3.869789809,-0.4028702555 C,-0.144154339,-1.7062864629,0.3249930349 C,-1.1132993606,-2.8208546286,0.7169047591 C,-0.6430071313,-1.0296724617,-0.9652075933 C,-1.4626314988,-3.2520787091,-1.7562001332 H,-0.0906738608,-4.3099000192,-0.4658735315 H,0.8124101263,-2.1900806106,0.0994819864 H,-2.1306362685,-2.4358028778,0.835713624 H,-1.6869343694,-0.746704129,-0.7959658794 232 H,-2.5080501758,-2.9160863278,-1.726506092 H,0.4756049978,-2.3687971194,-2.2161623119 H,-1.7875734537,-4.6796289904,-0.1582158173 H,-0.8040493033,-3.2586679499,1.6713818222 H,-1.3897328044,-4.0046534011,-2.5468876443 N,0.2181452319,-0.6846235906,1.3214779863 N,0.1254110597,0.189759712,-1.2532328099 C,-0.5482256662,-0.1437278237,2.1882348438 H,-0.0641170554,0.5958515261,2.8282206442 C,-0.4305610874,1.2491294936,-1.7222291036 H,0.2450854128,2.0924307666,-1.8502577828 B,1.7121906658,-0.1276176315,0.9669602282 B,1.6851648759,0.2279790466,-0.7202928373 O,2.3675950834,-0.7562670055,-1.5523266573 O,2.6271169257,-1.2091979046,1.3290532344 O,2.1973115528,1.5688954991,-1.0052696785 O,1.9601413939,1.0213854698,1.8283782468 C,3.3929407383,-1.8174783938,0.3979237475 C,5.0374145111,-3.2301504285,-1.3990531987 C,4.3467954204,-2.7334982923,0.8503496822 C,3.2667527308,-1.6020229848,-0.9979788152 C,4.0938265838,-2.3185163362,-1.8665434961 C,5.1666466702,-3.4369145315,-0.0285835679 H,4.4222379027,-2.8789591173,1.9241118496 H,3.9718249858,-2.1344058273,-2.930132129 H,5.8963015028,-4.1404425917,0.359961947 H,5.6640851482,-3.7684411225,-2.1031210418 C,1.8679813524,2.2660760576,1.3080073417 C,1.7511186695,4.9179236657,0.378399573 C,1.6791525914,3.3333507999,2.1884860347 C,1.9992962578,2.5368880135,-0.0764348526 C,1.9329869922,3.861759607,-0.5133323807 C,1.6214897586,4.6508447927,1.7379210789 H,1.5865134287,3.0988872927,3.2452575286 H,2.0391810405,4.0419291616,-1.5798047546 H,1.4764020083,5.4580562884,2.4489549512 H,1.7095961974,5.9369777398,0.0071072652 C,-1.9998269055,-0.3844893994,2.3621909521 C,-4.7318882836,-0.8307493569,2.6639891101 C,-2.4670088525,-1.1231107245,3.4516931628 C,-2.9016625887,0.1648342654,1.4458235344 C,-4.2669261511,-0.0635360841,1.5974449209 C,-3.8325745043,-1.3533669697,3.5926040719 H,-1.762170002,-1.5319094061,4.1695518428 H,-2.5346312522,0.7736011872,0.6230831342 H,-4.9641243096,0.3592156014,0.8808271701 233 H,-4.1945297889,-1.9425258448,4.4290653709 H,-5.7956684539,-1.0136222482,2.7775386822 C,-1.8403606536,1.5408397902,-2.021862349 C,-4.4841257807,2.3678972993,-2.413246292 C,-2.21034294,2.8792742829,-1.8101165503 C,-2.8070718476,0.6279443412,-2.4718743153 C,-4.1187372688,1.0465421438,-2.6674829033 C,-3.5268862375,3.2866274858,-1.986909806 H,-1.4562758365,3.5920865893,-1.4863845053 H,-2.5426468146,-0.3966148897,-2.7037340423 H,-4.8575880201,0.3367753435,-3.0245614032 H,-3.8027823726,4.3193864063,-1.8016853838 H,-5.5118707364,2.6836229805,-2.5621637418 IB-E,E[1,1]benzene (Intermediate dicoordinate 1,1-B2cat2-E,E-diimine 1 complex in benzene) boat_cydiimph2_EE_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1372708 Zero-point correction= 0.572215 (Hartree/Particle) Thermal correction to Energy= 0.603828 Thermal correction to Enthalpy= 0.604772 Thermal correction to Gibbs Free Energy= 0.509608 Sum of electronic and ZPE= -1696.565056 Sum of electronic and thermal Energies= -1696.533443 Sum of electronic and thermal Enthalpies= -1696.532498 Sum of electronic and thermal Free Energies= -1696.627663 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.908 129.808 200.290 H,3.1669486304,2.7616489388,1.3260843874 C,2.3525236294,3.0673110673,0.6606400033 C,0.8148184216,4.9695817426,0.0161851653 C,-0.0405987352,2.6258842634,0.0274665027 C,-0.3968593175,4.0829220648,0.3207146309 C,1.1211987787,2.2014602067,0.9469817133 C,2.0236248862,4.5492747625,0.8551782764 H,1.0614459172,4.8881656864,-1.0495139567 H,0.3056220609,2.5627808717,-1.0080202855 H,-0.6699503157,4.2158373749,1.3755472281 H,0.7910505217,2.3769464888,1.9814649712 H,1.8084871321,4.7384971935,1.9154602775 234 H,2.6748717615,2.8721690391,-0.367123524 H,0.5638422936,6.0166635068,0.2089223459 H,-1.2608433851,4.3753356181,-0.2851286407 H,2.8961965051,5.1556466028,0.5955750988 N,-1.1505857656,1.6552444893,0.1084509208 N,1.4179194275,0.7585094326,0.8154753317 C,-2.1310382269,1.8720933087,0.9009955098 H,-2.0923896114,2.7368953435,1.5678977987 C,1.9538235819,0.1956820414,1.8330728782 H,2.2156452035,0.8432071539,2.6783741412 B,-0.7574063103,0.1652187306,-0.6896633063 B,0.9738634669,0.135082778,-0.7309435825 O,1.7400609635,1.0241620296,-1.6398521962 O,1.6006337194,-1.1725830449,-0.8619429575 O,-1.482271035,0.0950896498,-1.9643617579 O,-1.326818082,-0.9024197997,0.1568900776 C,2.814040591,-0.9546589862,-1.4229223739 C,5.1065607382,-0.0664587801,-2.677124312 C,3.8680535776,-1.8365490077,-1.5552024465 C,2.8967856995,0.3628092324,-1.8991788272 C,4.0319906518,0.8276838309,-2.5330965825 C,5.0268669942,-1.3684246226,-2.1966104599 H,3.7912789826,-2.8486984256,-1.1719347962 H,4.0827800745,1.8450063937,-2.9075084672 H,5.8730360109,-2.0375075372,-2.3169772768 H,6.0129259944,0.2695179333,-3.1708622492 C,-2.2692740272,-1.5280576904,-0.5888528249 C,-4.1090788194,-2.4442063889,-2.4297058447 C,-3.087912134,-2.5764880293,-0.2247911464 C,-2.3576082261,-0.9322987348,-1.8574895712 C,-3.2728741168,-1.3737513941,-2.7925099074 C,-4.0199757228,-3.0317889783,-1.1732801396 H,-3.0187209099,-3.0147946246,0.7652583176 H,-3.3370023878,-0.9040160919,-3.768295536 H,-4.6766413886,-3.8575982412,-0.9180795543 H,-4.8328783053,-2.8174010812,-3.147591198 C,-3.3640287866,1.0702462946,0.9488828418 C,-5.766191585,-0.3295444523,1.045293293 C,-3.852839235,0.6082150255,2.1750813753 C,-4.0958702548,0.8576047517,-0.2224792306 C,-5.3023536668,0.1656213173,-0.1691309398 C,-5.0398851958,-0.1116294543,2.2168423012 H,-3.291482164,0.793004337,3.0865844561 H,-3.7159629329,1.2410211078,-1.1640096995 H,-5.8634181238,-0.0045779498,-1.0818124896 H,-5.4057285752,-0.495195858,3.1636131036 235 H,-6.698144845,-0.8845163141,1.08294244 C,2.2532706616,-1.2292527527,2.0345507307 C,2.8724101764,-3.8855003414,2.5853367453 C,1.364767629,-2.2422321321,1.6546046552 C,3.4281763458,-1.5489805291,2.7248265758 C,3.7487219319,-2.8769241374,2.9799618433 C,1.6795631238,-3.5657655141,1.9378661933 H,0.4372875722,-1.984595888,1.1532953147 H,4.0983467628,-0.7549295812,3.0436731322 H,4.672062821,-3.1230593446,3.4936428902 H,0.9905686533,-4.3520289595,1.6475768814 H,3.1133762943,-4.9232269422,2.7941787315 IB-E,Z[1,1]benzene (Intermediate dicoordinate 1,1-B2cat2-E,Z-diimine 1 complex in benzene) boat_cydiimph2_EZ_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1350779 Zero-point correction= 0.572155 (Hartree/Particle) Thermal correction to Energy= 0.604031 Thermal correction to Enthalpy= 0.604976 Thermal correction to Gibbs Free Energy= 0.507754 Sum of electronic and ZPE= -1696.562923 Sum of electronic and thermal Energies= -1696.531046 Sum of electronic and thermal Enthalpies= -1696.530102 Sum of electronic and thermal Free Energies= -1696.627324 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.035 129.791 204.621 H,1.1829000809,-3.3723162139,1.456230347 C,0.4408379742,-2.6822193436,1.8723649421 C,-1.7805709854,-2.5131632424,3.0864685965 C,-1.2245501981,-0.8861021939,1.3031028563 C,-2.3638382977,-1.688182343,1.9317444636 C,-0.1596682091,-1.8485431187,0.7388760266 C,-0.6728582616,-3.4497110178,2.5931857362 H,-1.3748435559,-1.836578323,3.8488888494 H,-0.7555575987,-0.3056789891,2.1053648678 H,-2.8258282852,-2.3638651033,1.2055114178 H,-0.6766459301,-2.5263362943,0.0448355361 H,-1.1083786076,-4.1889886176,1.9074808518 H,0.9591680788,-2.0120118128,2.5635727833 H,-2.5780897063,-3.091394297,3.5621799937 236 H,-3.1396412651,-1.0041726363,2.2902507474 H,-0.2474419354,-4.0077453382,3.4324405535 N,-1.52309353,0.1239172147,0.2751793165 N,0.8415228798,-1.0883668421,-0.0395874363 C,-2.4278901364,0.0797683182,-0.6199526053 H,-2.4430657066,0.9362236992,-1.2966423857 C,1.344956729,-1.6771031805,-1.0576708099 H,1.0915833409,-2.733745309,-1.2076314259 B,-0.3503640277,1.3720815,0.3306592077 B,1.1420792025,0.5382392816,0.6081709094 O,1.4917113834,0.2089984862,2.0036763279 O,2.3756735121,0.9927388171,-0.0047857087 O,-0.8276577735,2.2567819614,1.4061505838 O,-0.5299276636,2.118826472,-0.9224129923 C,3.3756881396,0.5727585613,0.8089476278 C,5.0483262057,-0.3592539302,2.7944369858 C,4.7347505124,0.5722313815,0.5672493384 C,2.8454201166,0.1075007926,2.0214567053 C,3.6634685482,-0.3600242919,3.0310657727 C,5.5718421682,0.0945170228,1.5889374354 H,5.1273431849,0.9278996169,-0.3795751368 H,3.2456584346,-0.7070947887,3.9704753946 H,6.6456672875,0.0807185447,1.4314740326 H,5.717969184,-0.7209278585,3.5682910489 C,-1.2795627305,3.2086835043,-0.6020333927 C,-2.7491848618,5.2667120236,0.4989493171 C,-1.8197795911,4.1520622566,-1.4525004747 C,-1.4640566713,3.2785478286,0.7886658392 C,-2.1977200631,4.3019369366,1.3580458436 C,-2.5651388794,5.1945931053,-0.8765499009 H,-1.6638830392,4.0858602882,-2.5241865584 H,-2.3319066975,4.3521379612,2.4332225866 H,-3.000188275,5.9535458436,-1.518849468 H,-3.3272725057,6.0825398348,0.9212770218 C,-3.4106356446,-1.00754464,-0.85528742 C,-5.2425235756,-3.0559134037,-1.3047008549 C,-4.7343027143,-0.8616580746,-0.4357335951 C,-3.0131187209,-2.1631482399,-1.5317969675 C,-3.9302710707,-3.1868904764,-1.7525574043 C,-5.6438762416,-1.8919961754,-0.6522677485 H,-5.0417008143,0.0463634196,0.0742669915 H,-1.9910642773,-2.2540206781,-1.8892467993 H,-3.6198339474,-4.0852612234,-2.2760814398 H,-6.6683394799,-1.7847315392,-0.3113107791 H,-5.9550915258,-3.8567734442,-1.472722458 C,2.196258476,-1.0860827778,-2.0994340477 237 C,3.7622432978,-0.1036883971,-4.1789278135 C,1.9650825557,0.2028953447,-2.5955409486 C,3.1865282891,-1.8902559355,-2.6737327855 C,3.9836857367,-1.3919565175,-3.6974762804 C,2.7473786237,0.6845831283,-3.6371862565 H,1.1766613421,0.8172311345,-2.1709101342 H,3.3412272911,-2.9000660639,-2.302926839 H,4.7667608119,-2.0092492785,-4.1248547891 H,2.5674288774,1.6819608267,-4.0240545166 H,4.3746947357,0.2842138441,-4.986900682 IB-Z,E[1,1]benzene (Intermediate dicoordinate 1,1-B2cat2-Z,E-diimine 1 complex in benzene) boat_cydiimph2_ZE_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1391098 Zero-point correction= 0.572705 (Hartree/Particle) Thermal correction to Energy= 0.604232 Thermal correction to Enthalpy= 0.605176 Thermal correction to Gibbs Free Energy= 0.509874 Sum of electronic and ZPE= -1696.566405 Sum of electronic and thermal Energies= -1696.534878 Sum of electronic and thermal Enthalpies= -1696.533934 Sum of electronic and thermal Free Energies= -1696.629235 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.161 129.441 200.579 H,-2.9092119804,1.5572842941,-2.0595732779 C,-2.6569543735,1.8200780752,-1.0268838449 C,-2.3074047995,3.7287592371,0.5950220681 C,-0.8288933689,1.7218531776,0.7053472685 C,-0.8767138558,3.2423224542,0.8478097154 C,-1.2297259839,1.3412062153,-0.7339714064 C,-2.7785381914,3.3284816686,-0.80457561 H,-2.9754776389,3.2921635337,1.3475235596 H,-1.5656698807,1.2904062768,1.3893022419 H,-0.2127412497,3.7264533429,0.1198577567 H,-0.5310765252,1.8384111093,-1.4175995872 H,-2.1722408037,3.8547738798,-1.5536001517 H,-3.3391767685,1.272397844,-0.3666105021 H,-2.3538184364,4.8149527538,0.715624641 H,-0.5348974779,3.5258654605,1.8487119415 238 H,-3.8158039696,3.6386841624,-0.9606816378 N,0.4463761876,1.068023687,1.0628495253 N,-1.1526059334,-0.1126493477,-0.9285221175 C,1.5433876352,1.716975763,0.9461185183 H,1.5178390406,2.7264870256,0.5293526256 C,-0.854035016,-0.6450147822,-2.0505016811 H,-0.8840359905,-1.7353085673,-2.063360836 B,0.2659978956,-0.6590461498,1.2284097469 B,-1.2514634404,-1.0314845605,0.4674054474 O,-2.5433408749,-0.6693998433,1.0951723392 O,-1.4051410019,-2.4205680455,0.0161935426 O,0.4413690085,-1.05878729,2.6274063511 O,1.4160573743,-1.2200742255,0.495774283 C,-2.7324840121,-2.6929379838,0.0937837337 C,-5.463136732,-2.8348698252,0.4868993508 C,-3.4008630157,-3.8161179131,-0.3517899179 C,-3.4126795939,-1.6456965652,0.7351592936 C,-4.7774609834,-1.6957379466,0.9406221298 C,-4.7891793309,-3.8729114649,-0.1450700979 H,-2.8626921895,-4.6228128958,-0.8381699458 H,-5.2917829481,-0.8825469242,1.4421186172 H,-5.3405038847,-4.7440235355,-0.48455463 H,-6.536117266,-2.9022996611,0.6361241083 C,2.1414815941,-1.9201885211,1.3976194576 C,3.316759638,-3.1601709083,3.5677659609 C,3.3165185664,-2.6145787702,1.1956019084 C,1.5533090888,-1.8324607466,2.6704460651 C,2.1226011435,-2.4453095259,3.7685924981 C,3.9022901695,-3.2398867298,2.309939078 H,3.7694408055,-2.6600830578,0.2109963473 H,1.6599187004,-2.3684350553,4.7469010043 H,4.8245759026,-3.7976793078,2.1808187689 H,3.7839917983,-3.6589699932,4.4112224222 C,2.8665948124,1.2270679239,1.3583590133 C,5.4030012486,0.396850736,2.1438898482 C,3.9503402585,1.3689152029,0.4842657625 C,3.0640331325,0.7051709814,2.6391155992 C,4.3360554396,0.2985646086,3.0312341476 C,5.2105749048,0.9309383864,0.8691531895 H,3.7979577619,1.8018595863,-0.5008595861 H,2.2205162287,0.6257116924,3.3168976695 H,4.4839729889,-0.1157393232,4.0227515242 H,6.0456244717,1.0137149233,0.1812873165 H,6.3902758421,0.0622716529,2.445947031 C,-0.4571653513,0.0805446966,-3.2812144605 C,0.3212182652,1.3888123867,-5.6149013557 239 C,0.7835598867,0.7230357375,-3.3429877018 C,-1.2974497677,0.0766763175,-4.3969048994 C,-0.9097534888,0.7401499533,-5.5576540246 C,1.1697874994,1.3741176151,-4.5098047554 H,1.4452347047,0.687246522,-2.4816699644 H,-2.2519463477,-0.4396362571,-4.3518476484 H,-1.5684161464,0.7442345784,-6.4198802189 H,2.1363051562,1.865061385,-4.5585363231 H,0.6236314683,1.8989008969,-6.5236672552 IB-Z,Z[1,1]benzene (Intermediate dicoordinate 1,1-B2cat2-Z,Z-diimine 1 complex in benzene) cfc_boat_cydiimph2_ZZ_b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1408086 Zero-point correction= 0.573038 (Hartree/Particle) Thermal correction to Energy= 0.604620 Thermal correction to Enthalpy= 0.605564 Thermal correction to Gibbs Free Energy= 0.508721 Sum of electronic and ZPE= -1696.567771 Sum of electronic and thermal Energies= -1696.536188 Sum of electronic and thermal Enthalpies= -1696.535244 Sum of electronic and thermal Free Energies= -1696.632087 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.405 129.188 203.824 H,0.0862549861,3.0039678612,1.9437282432 C,0.0976351272,1.9507323823,2.2430930392 C,1.1518107642,0.2312461897,3.7795254356 C,0.4365700738,-0.4082758861,1.4946189367 C,1.4950069828,-0.6480221058,2.5701026657 C,0.4804736864,1.0682741309,1.0503285077 C,1.0842628382,1.7121261191,3.3905043899 H,0.1839781076,-0.0803194667,4.1915596228 H,-0.5442516399,-0.5926739438,1.9492016315 H,2.4941935448,-0.3884101088,2.2068836127 H,1.5126844864,1.2835185598,0.7503769498 H,2.0843777778,2.0495918246,3.0845112949 H,-0.9227066896,1.6926680208,2.5444003864 H,1.8981574017,0.0820746019,4.5652175596 H,1.5050484798,-1.7074214066,2.8454469588 H,0.7953545038,2.3171740454,4.2548439272 N,0.4226917692,-1.2553751075,0.2947685167 240 N,-0.4020235041,1.2589511188,-0.1036179503 C,1.4222640765,-1.7057128379,-0.3541458118 H,1.1615524686,-2.2937408847,-1.2365292096 C,-0.07622473,1.9477066926,-1.1323237276 H,-0.8126180382,1.9175240902,-1.9368176413 B,-1.1815182528,-1.3848490074,-0.2628501762 B,-1.7967141977,0.2435933871,-0.1587345257 O,-2.5177055763,0.5891907688,1.0814751913 O,-2.5969154163,0.7859785006,-1.2569134699 O,-1.7970984441,-2.3515452892,0.6653163671 O,-1.0848894798,-2.0662889686,-1.5573846329 C,-3.4777156541,1.6450864634,-0.6776985986 C,-5.1197034503,3.1934468577,0.9121592231 C,-4.3443402193,2.5248429848,-1.2948049662 C,-3.4257908545,1.528315229,0.7204394086 C,-4.2383359123,2.2941089635,1.5339021799 C,-5.1720804416,3.3065526695,-0.4721812218 H,-4.3803271143,2.599571973,-2.3765385129 H,-4.1949257322,2.1915354945,2.6131848666 H,-5.8635636358,4.0075816566,-0.9286247126 H,-5.770765981,3.8074713777,1.5263299893 C,-1.3449616099,-3.3764837033,-1.3044297087 C,-1.984588695,-5.8872583821,-0.3534094734 C,-1.2445768342,-4.4480370959,-2.1692533118 C,-1.7605009202,-3.5435877726,0.0270871368 C,-2.0850583355,-4.7926116613,0.5211824076 C,-1.5732781929,-5.7197606095,-1.6702355868 H,-0.9280024924,-4.3024894502,-3.1968088569 H,-2.409814046,-4.9117099461,1.5493202698 H,-1.5053688781,-6.5812386015,-2.3269392683 H,-2.2349305209,-6.8792956608,0.009164372 C,2.8601665648,-1.474367995,-0.0642122874 C,5.5547787017,-1.0169103903,0.4739294653 C,3.6293432228,-2.4730730038,0.5367404333 C,3.4496924219,-0.2609588679,-0.4294805776 C,4.7953950719,-0.0335577753,-0.1552962857 C,4.9724039583,-2.2367219214,0.8132129259 H,3.1711603684,-3.4207391625,0.8034578135 H,2.8585694038,0.5002552989,-0.9324610388 H,5.2460556706,0.9127683513,-0.4370246439 H,5.565407067,-3.0074692303,1.2945585844 H,6.6027233311,-0.8375849275,0.6912799905 C,1.1691445342,2.6827268424,-1.4184112588 C,3.5545573074,3.9288356535,-2.1765842384 C,1.5881928576,2.6660914401,-2.7566449613 C,1.9409194305,3.368716974,-0.4696225584 241 C,3.1246534804,3.9894438216,-0.8520883791 C,2.7828625153,3.2695424384,-3.1306283049 H,0.9762798524,2.1606963498,-3.4985862144 H,1.6068885994,3.4452767009,0.5588666415 H,3.7104451654,4.5270197194,-0.1139159021 H,3.1052934072,3.2343339161,-4.1657377209 H,4.4825054823,4.4104577005,-2.4676442097 IB-E,E[1,2]benzene (Intermediate dicoordinate 1,2-B2cat2-E,E-diimine 1 complex in benzene) boat_cydiimph2_EE_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1513138 Zero-point correction= 0.572968 (Hartree/Particle) Thermal correction to Energy= 0.604065 Thermal correction to Enthalpy= 0.605010 Thermal correction to Gibbs Free Energy= 0.510628 Sum of electronic and ZPE= -1696.578346 Sum of electronic and thermal Energies= -1696.547248 Sum of electronic and thermal Enthalpies= -1696.546304 Sum of electronic and thermal Free Energies= -1696.640686 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.057 129.061 198.644 H,-2.5299161258,2.107469694,-2.383557495 C,-2.2977270024,2.3525872288,-1.3419587449 C,-1.9395545038,4.2408013836,0.3024855015 C,-0.572172241,2.1581834567,0.4542944286 C,-0.5525496882,3.6774609356,0.6198373286 C,-0.912292007,1.7909241937,-0.9922109879 C,-2.3609212743,3.8645498326,-1.1185671757 H,-2.6645502035,3.8377073933,1.02018795 H,-1.3655333357,1.7614324235,1.0980762371 H,0.1784566999,4.1349172576,-0.0591712669 H,-0.1528324945,2.2451727471,-1.6473656434 H,-1.6949922849,4.363043434,-1.8357020335 H,-3.0329431242,1.8333982405,-0.7146990988 H,-1.9362921835,5.327740724,0.4245248322 H,-0.2513797838,3.9198215247,1.643633711 H,-3.3738167308,4.2219729324,-1.3254089987 N,0.6438962584,1.4595012564,0.900280771 N,-0.9091602232,0.3303291791,-1.2252444661 242 C,1.8001246103,1.9833390051,0.705240069 H,1.8613512478,2.8998038836,0.114289547 C,-0.7786593922,-0.0215539207,-2.4574336353 H,-0.4681206112,0.7534329807,-3.1660030425 B,0.2149004013,-0.0707942629,1.316258995 B,-0.9145982489,-0.6498319405,0.1149355771 O,-2.3030250082,-0.6081073486,0.5522672838 O,-0.3994966947,0.0869277837,2.6305844612 O,-0.5419769012,-1.9951011677,-0.2910175426 O,1.398456195,-0.8949079505,1.4143789881 C,-1.6437307384,-0.378053812,2.8876663538 C,-4.227203122,-1.2359775262,3.5858555582 C,-2.033116259,-0.484615228,4.2236215491 C,-2.5753178773,-0.716654211,1.8791603201 C,-3.8508549067,-1.1406739938,2.2492335316 C,-3.3104543508,-0.9072491537,4.5793396565 H,-1.2963405198,-0.2208131175,4.9760957971 H,-4.5408260272,-1.3928667568,1.4495937062 H,-3.5819494344,-0.9792246169,5.6277236913 H,-5.2272546484,-1.569644969,3.8434755571 C,1.7527112153,-1.673259995,0.368846708 C,2.5292001033,-3.4165865118,-1.6774299836 C,3.099812002,-1.959125533,0.1554329708 C,0.7771637988,-2.251588084,-0.4718874664 C,1.1796280883,-3.1242563817,-1.4811349495 C,3.49078183,-2.8267931008,-0.8635671357 H,3.8264413077,-1.4955217043,0.8177428462 H,0.4090346197,-3.5734756901,-2.101683236 H,4.5442021918,-3.0438416209,-1.0108432762 H,2.8210266006,-4.1025009025,-2.4665423915 C,3.0667323135,1.4903886999,1.248945684 C,5.5264604914,0.6712767182,2.2637552599 C,3.1342702727,0.878907374,2.5076770762 C,4.2398747521,1.7183438071,0.5200809929 C,5.4651280153,1.2913054427,1.0166111919 C,4.3651561877,0.4777339319,3.0114287924 H,2.2248330405,0.7310459622,3.0801182998 H,4.1846450601,2.2141524427,-0.4453214574 H,6.3699744829,1.4493820542,0.4394456004 H,4.4184027465,0.0075919233,3.9875751255 H,6.4840787602,0.3484935681,2.6601833003 C,-1.0809335504,-1.3216957134,-3.0468890363 C,-1.6698461393,-3.7344159269,-4.2996457503 C,-0.4143960909,-1.6837577834,-4.2246273442 C,-2.0759286286,-2.1560697594,-2.5191096979 C,-2.3666634265,-3.3582821463,-3.1514739365 243 C,-0.6941225745,-2.8967464637,-4.8396359713 H,0.3399150632,-1.0205908882,-4.6396254835 H,-2.610626615,-1.8522333302,-1.625324738 H,-3.1359024553,-4.0064648795,-2.74560212 H,-0.160920995,-3.1867788721,-5.7386791221 H,-1.8977599539,-4.6790841223,-4.783522003 IB-E,Z[1,2]benzene (Intermediate dicoordinate 1,2-B2cat2-E,Z-diimine 1 complex in benzene) boat_cydiimph2_EZ_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1466478 Zero-point correction= 0.573229 (Hartree/Particle) Thermal correction to Energy= 0.604404 Thermal correction to Enthalpy= 0.605348 Thermal correction to Gibbs Free Energy= 0.510165 Sum of electronic and ZPE= -1696.573418 Sum of electronic and thermal Energies= -1696.542244 Sum of electronic and thermal Enthalpies= -1696.541300 Sum of electronic and thermal Free Energies= -1696.636482 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.269 128.991 200.328 H,-2.0590984552,1.5803404459,-2.3040067483 C,-1.9135868259,1.8486255388,-1.252237168 C,-1.6493814243,3.7830730556,0.3674207523 C,-0.3512161352,1.696107006,0.6852893982 C,-0.2941639914,3.2189945488,0.8068023845 C,-0.5670091277,1.2867293583,-0.7772445934 C,-1.9678060012,3.3680164797,-1.0709396745 H,-2.4332902021,3.4121538367,1.0394552013 H,-1.2320923551,1.3659891176,1.2480980475 H,0.4956932353,3.63962146,0.1764290383 H,0.2412590136,1.728121268,-1.3777200653 H,-1.240474428,3.8361550977,-1.7475921405 H,-2.7054266283,1.3542720858,-0.6766200132 H,-1.6409849526,4.8734506424,0.4530968138 H,-0.072078467,3.4900592376,1.8437364302 H,-2.955868076,3.7343763226,-1.3644291119 N,0.7376565714,0.9015863819,1.2659897192 N,-0.5434589687,-0.1795969423,-0.9796460076 C,1.9794300636,1.1895352448,1.3221299389 H,2.5916940838,0.4295451713,1.8110499326 244 C,-0.1948570496,-0.5609681564,-2.1583848337 H,0.2466427143,0.1938429443,-2.8183127162 B,0.1370327415,-0.5574616491,1.6942484413 B,-0.8169360389,-1.1372681195,0.3692504784 O,-2.2532954378,-1.0123918031,0.5620969021 O,-0.6531796633,-0.2818328638,2.8871554625 O,-0.4522243065,-2.504531345,0.0523442561 O,1.2795779831,-1.388440913,2.032598201 C,-1.9730048536,-0.5705100397,2.9462080154 C,-4.7265585439,-1.0577489477,3.2382784414 C,-2.5973746123,-0.4744594557,4.1914797901 C,-2.7539690459,-0.9248969849,1.821234251 C,-4.1180886513,-1.1611637054,1.9911418448 C,-3.9591339799,-0.7134715251,4.3466908584 H,-1.9720481771,-0.2042088284,5.036806904 H,-4.6870386769,-1.4315574325,1.1066694695 H,-4.4124285629,-0.6314639419,5.3294201993 H,-5.7900398398,-1.2495039273,3.3384117663 C,1.7077197726,-2.3077312825,1.1364135667 C,2.6670892636,-4.2840322879,-0.6072032447 C,3.0285502775,-2.7486808834,1.2106639115 C,0.8496638952,-2.8669582752,0.1616319072 C,1.3464799252,-3.8481682635,-0.6956204902 C,3.5122518931,-3.7304356648,0.3484656169 H,3.6609571263,-2.3134246377,1.9791816226 H,0.6629944121,-4.2661748068,-1.4296504799 H,4.5428890783,-4.0605748986,0.4319698185 H,3.0267072543,-5.0531592093,-1.2833421485 C,2.6474317563,2.3961108255,0.7769256204 C,3.9117789321,4.6563151963,-0.2510294603 C,2.8971920146,2.4946679577,-0.5944397619 C,3.0646842909,3.4141439908,1.6373641643 C,3.6854365595,4.5462894462,1.1193809335 C,3.5263708573,3.6263992347,-1.1055355944 H,2.6098826036,1.6798610206,-1.2532596684 H,2.8843195384,3.3256860095,2.7045058534 H,3.9942092955,5.3432252138,1.7878490402 H,3.7192100722,3.7010218556,-2.1707707314 H,4.3983691839,5.5397377512,-0.6512547838 C,-0.4016430464,-1.8763285817,-2.7598447001 C,-0.8037637952,-4.3094152588,-4.0470228423 C,0.4874547479,-2.3002098077,-3.7554216335 C,-1.5168694069,-2.6604944204,-2.4353822153 C,-1.7145936454,-3.8721753671,-3.085438987 C,0.2986540688,-3.5243402591,-4.3834593656 H,1.3377642894,-1.676370753,-4.0175897432 245 H,-2.2162570938,-2.3102444573,-1.6834493278 H,-2.5782543144,-4.4800374014,-2.837918258 H,1.0009701273,-3.8625685398,-5.1377928478 H,-0.9605228917,-5.2610521091,-4.5453255971 IB-Z,E[1,2]benzene (Intermediate dicoordinate 1,2-B2cat2-Z,E-diimine 1 complex in benzene) boat_cydiimph2_ZE_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1510071 Zero-point correction= 0.573341 (Hartree/Particle) Thermal correction to Energy= 0.604663 Thermal correction to Enthalpy= 0.605607 Thermal correction to Gibbs Free Energy= 0.508941 Sum of electronic and ZPE= -1696.577666 Sum of electronic and thermal Energies= -1696.546344 Sum of electronic and thermal Enthalpies= -1696.545400 Sum of electronic and thermal Free Energies= -1696.642066 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.432 128.980 203.452 H,-2.6400122365,1.8187779876,-2.0236935469 C,-2.2904385562,2.0294950626,-1.0077619136 C,-1.5286275479,3.8508265337,0.5766643828 C,-0.4391778814,1.6110874605,0.6338582544 C,-0.2000380296,3.1131302223,0.7744228019 C,-0.953205001,1.3126880669,-0.7831189909 C,-2.1320669816,3.5360211299,-0.793715702 H,-2.2276373975,3.5451783327,1.3649426662 H,-1.224690015,1.3364156971,1.3460562004 H,0.5164314789,3.4679333816,0.0223203267 H,-0.2143511688,1.6983190939,-1.4936441725 H,-1.480617295,3.9435593001,-1.5781670908 H,-3.0206688115,1.6051252604,-0.3089464896 H,-1.3726053248,4.9280006859,0.6852678801 H,0.2222490884,3.3224328995,1.7624557362 H,-3.1042076183,4.0255026784,-0.9023044013 N,0.6914122398,0.7282999629,0.9794309752 N,-1.1200567504,-0.1344493863,-1.000833966 C,1.8979158052,1.1454621957,0.8528623947 H,2.0624589667,2.1196302792,0.3867875181 C,-1.0863686151,-0.6446626305,-2.1738490939 246 H,-1.3136229496,-1.7093561041,-2.2223939676 B,0.0883892823,-0.7846876207,1.3528161594 B,-1.2719703928,-1.0719039084,0.3387517902 O,-2.5453923849,-0.6647874333,0.913059901 O,-0.2751572356,-0.6753996059,2.7635583788 O,-1.3351926221,-2.4490306077,-0.1268980857 O,1.1543842517,-1.7451424245,1.174480713 C,-1.5678963202,-0.5894560175,3.1544024052 C,-4.1878660658,-0.3540614165,4.1495219105 C,-1.8166730517,-0.4791972877,4.5243719644 C,-2.6680794707,-0.5885012554,2.2623049249 C,-3.9574352352,-0.4660538675,2.7821407855 C,-3.1081781834,-0.3638209381,5.0274580629 H,-0.953962987,-0.4876142135,5.1835452198 H,-4.7776796513,-0.4690310751,2.0705865634 H,-3.2645419362,-0.2819739302,6.0983387986 H,-5.2036102081,-0.2649101141,4.5210870911 C,1.0492469896,-2.7432312785,0.2707998384 C,0.9734257181,-4.9120087375,-1.5121930437 C,2.2025037699,-3.4695402336,-0.0295029155 C,-0.1688512061,-3.1066407537,-0.3483725993 C,-0.1822041697,-4.1882906899,-1.2298579328 C,2.1739466987,-4.5457592332,-0.9119228075 H,3.1215748917,-3.164339386,0.4625602754 H,-1.1358549789,-4.4521923355,-1.678560051 H,3.0861468048,-5.0951091842,-1.1219840142 H,0.9307812098,-5.7524111492,-2.1974817063 C,3.1063127362,0.4649698541,1.3223767374 C,5.4798791915,-0.6868176775,2.209298497 C,4.3068638248,0.7174995239,0.6479372321 C,3.1048085122,-0.3392361463,2.4699384313 C,4.293859418,-0.9068392721,2.9093378359 C,5.4883284576,0.1264181659,1.0775525242 H,4.3071793068,1.367709621,-0.2231198368 H,2.1787477342,-0.502612904,3.011240112 H,4.2953368889,-1.5256121705,3.8003419212 H,6.4133942623,0.3073070216,0.5405667903 H,6.4035506153,-1.1398352836,2.5556760634 C,-0.7737342981,0.0657813832,-3.4355372346 C,-0.1978178795,1.3237314454,-5.8554879369 C,0.4941628946,0.6145758378,-3.6557031785 C,-1.7422802854,0.1259896423,-4.44127719 C,-1.4564921511,0.7667898485,-5.6429247022 C,0.7786980734,1.2391755328,-4.865302283 H,1.2583184664,0.5263380495,-2.8880306615 H,-2.7180732167,-0.3218866551,-4.2760888917 247 H,-2.2153553426,0.8229377063,-6.4163228255 H,1.7662561215,1.6546647533,-5.0372052507 H,0.026127694,1.814628281,-6.7969175214 IB-Z,Z[1,2]benzene (Intermediate dicoordinate 1,2-B2cat2-Z,Z-diimine 1 complex in benzene) boat_cydiimph2_ZZ_1-2-b2cat2_benzene M062X/6-31G(d,p) E(RM062X) = -1697.150696 Zero-point correction= 0.573982 (Hartree/Particle) Thermal correction to Energy= 0.605063 Thermal correction to Enthalpy= 0.606007 Thermal correction to Gibbs Free Energy= 0.511117 Sum of electronic and ZPE= -1696.576714 Sum of electronic and thermal Energies= -1696.545633 Sum of electronic and thermal Enthalpies= -1696.544689 Sum of electronic and thermal Free Energies= -1696.639579 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 379.683 128.684 199.714 H,-0.8243832973,-1.5831768375,-3.0736109073 C,-0.5134760477,-2.0369319669,-2.127084203 C,-1.0087633176,-3.8624753064,-0.4323427266 C,-0.1189806907,-1.6773384821,0.3034429816 C,-1.0667772686,-2.813193867,0.6861338132 C,-0.6171156684,-1.0107306823,-0.9932654684 C,-1.3797448098,-3.2550503447,-1.7897976269 H,0.0062453152,-4.2757610619,-0.4851364687 H,0.8497492448,-2.1391089517,0.0867300873 H,-2.0944578779,-2.4539153266,0.7992932427 H,-1.6683651434,-0.7434045979,-0.8371966594 H,-2.4356012717,-2.9505967618,-1.77024104 H,0.5391920613,-2.3183999503,-2.2404912307 H,-1.6818968706,-4.69138984,-0.1952455222 H,-0.7558032031,-3.2443851921,1.6428983172 H,-1.2802204989,-4.0059954045,-2.578879821 N,0.2119174109,-0.6445858171,1.2960397675 N,0.1397987471,0.2157240397,-1.2735448363 C,-0.5693606436,-0.1153141944,2.1550698836 H,-0.0981107436,0.6407952561,2.7859692426 C,-0.4230066019,1.2836174721,-1.7092148796 H,0.2528310325,2.128132807,-1.8291917364 B,1.7186126366,-0.064929192,0.9579420995 248 B,1.7173522796,0.2598830804,-0.7364995148 O,2.3827887712,-0.7454893535,-1.5427424747 O,2.6276429126,-1.1300492811,1.3505248081 O,2.2121006465,1.5935967955,-1.0437686227 O,1.9090770471,1.0987163,1.8043419857 C,3.3576398936,-1.8062787319,0.434124543 C,4.9102396026,-3.3574292924,-1.3243791238 C,4.2576450789,-2.7616538904,0.9113403229 C,3.239736928,-1.6236693402,-0.964886413 C,4.0196818309,-2.4083333241,-1.8159298503 C,5.0317599243,-3.5330038846,0.0506662954 H,4.3281126159,-2.8760914958,1.9886716334 H,3.9057258601,-2.2407778623,-2.8827487453 H,5.7232711936,-4.2644449472,0.4565401786 H,5.5049815011,-3.9483887865,-2.0134631479 C,1.8597546723,2.334350465,1.2559678437 C,1.809627538,4.9699142675,0.2777810933 C,1.6714929134,3.4205740404,2.1119382558 C,2.0254287533,2.577881355,-0.128973767 C,1.9945206805,3.8956704206,-0.5896658052 C,1.6449932137,4.7292847884,1.637681228 H,1.5601526904,3.2047940014,3.1705763588 H,2.1389970189,4.0515423255,-1.6552957848 H,1.5022054077,5.5514996597,2.3314788335 H,1.7999867847,5.9830474901,-0.1110386827 C,-2.0160464006,-0.3924155473,2.3302745974 C,-4.7360131466,-0.9134850096,2.6354035212 C,-2.4626974287,-1.1552375853,3.4114785101 C,-2.936313968,0.1415963469,1.4234632204 C,-4.2942416538,-0.1238941154,1.576461666 C,-3.8206238202,-1.4223346281,3.5546694947 H,-1.745927299,-1.5540020473,4.1231232189 H,-2.592079231,0.7720797986,0.6071489722 H,-5.0036632664,0.2905656109,0.8674405887 H,-4.1642959593,-2.0290299396,4.3860999704 H,-5.794314354,-1.1237907591,2.7507258774 C,-1.8445695998,1.571623305,-1.9671014602 C,-4.5130762023,2.3477466777,-2.2730706137 C,-2.2514948699,2.8729300165,-1.6343389949 C,-2.7853694317,0.6747019262,-2.4929067954 C,-4.1103280766,1.0670337906,-2.6471001803 C,-3.5814355393,3.2523766647,-1.7684861514 H,-1.516574945,3.5760593973,-1.2505416524 H,-2.483504101,-0.3161464535,-2.812302183 H,-4.8293876637,0.3707710792,-3.0657290885 H,-3.8874911525,4.2549774059,-1.4896411672 249 H,-5.5501421634,2.6452675285,-2.3904981274 TS-E,E[1,1]MeOH (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,E- diimine 1 complex in MeOH) cydiimph2_EE_b2cat2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1304131 Zero-point correction= 0.571244 (Hartree/Particle) Thermal correction to Energy= 0.602192 Thermal correction to Enthalpy= 0.603136 Thermal correction to Gibbs Free Energy= 0.509323 Sum of electronic and ZPE= -1696.559169 Sum of electronic and thermal Energies= -1696.528221 Sum of electronic and thermal Enthalpies= -1696.527277 Sum of electronic and thermal Free Energies= -1696.621090 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.881 128.071 197.446 H,1.1386244956,4.4554925418,0.6706319889 C,1.1815692631,3.9508477261,-0.2993146081 C,0.8606348326,4.2751177356,-2.8157967252 C,0.1686114662,2.1643194194,-1.7447514692 C,-0.1725738519,3.1373428082,-2.8651652934 C,0.0767271374,2.9055326409,-0.3917450875 C,0.9366124189,4.9529886876,-1.4401481417 H,1.8453968948,3.8601569364,-3.0657403405 H,1.2004278301,1.8351297068,-1.891659093 H,-1.1851825309,3.5375035726,-2.7343921732 H,-0.8699453049,3.4520163053,-0.3811028082 H,-0.0046276766,5.4839667394,-1.2476254255 H,2.1655936041,3.4865245049,-0.4014263897 H,0.6242354707,5.0190543968,-3.582390472 H,-0.1335992082,2.6244508554,-3.8308165852 H,1.7314796796,5.7047487321,-1.4434635003 N,-0.6377738453,0.9226733632,-1.6504661543 N,-0.0343989479,1.8823812052,0.6884881474 C,-1.9249763679,1.0798962591,-1.407877429 H,-2.3095435655,2.0973036098,-1.3677654564 C,-1.2268261447,1.8648063301,1.246750563 H,-1.8331704972,2.7491934849,1.0665551322 B,0.2469871114,-0.1798777707,-1.0964840294 B,0.9539065861,0.7553212575,0.5267930861 O,2.3089671796,1.2017811332,0.1900138099 250 O,1.0985692728,-0.2584380067,1.5592293574 O,1.4483516081,-0.5044970103,-1.8654423321 O,-0.3261117171,-1.4355194927,-0.6626247521 C,2.4120192873,-0.6280695898,1.517428105 C,5.1052288111,-1.0209086929,1.0924245932 C,3.0087451554,-1.7157042434,2.12151986 C,3.1348409298,0.2497767751,0.7001170361 C,4.4858291847,0.0782766806,0.4737256359 C,4.3835661272,-1.899258808,1.8947271709 H,2.431428203,-2.3995056909,2.73497375 H,5.0356578424,0.7606064563,-0.1659318236 H,4.8858139495,-2.7463049423,2.3510397208 H,6.1655211307,-1.1886578992,0.9320234309 C,0.6583674245,-2.3629147137,-0.8395269733 C,2.9216589769,-3.844430984,-1.3536229766 C,0.6954198301,-3.6633667775,-0.3798209294 C,1.7237122685,-1.8018583236,-1.5549838771 C,2.8731959051,-2.5198979982,-1.8193552676 C,1.8571399766,-4.404442202,-0.6530697353 H,-0.1356514396,-4.082039105,0.1782599948 H,3.7023832265,-2.0691197933,-2.3544831879 H,1.9255415097,-5.4290492307,-0.3017914936 H,3.8114718541,-4.4371851383,-1.5406422663 C,-2.8952322399,0.0009820717,-1.2729446423 C,-4.8261555583,-2.0004979845,-0.9549282205 C,-4.0125225824,0.2111985387,-0.4469655769 C,-2.7749230389,-1.2161052617,-1.9620949866 C,-3.7366407537,-2.2072685947,-1.8005266821 C,-4.9650612956,-0.7859804094,-0.281842893 H,-4.1119856692,1.1562933926,0.0813792544 H,-1.9402302802,-1.3686676513,-2.6383138493 H,-3.6384320409,-3.1431477668,-2.3417298992 H,-5.8149155455,-0.6180379171,0.3722716404 H,-5.5711094942,-2.780094967,-0.8290913294 C,-1.8339390883,0.9081113754,2.1727321529 C,-3.2908813868,-0.7532505761,3.8966967369 C,-1.7254562627,-0.4871364498,2.0706563542 C,-2.7171907799,1.4540773523,3.1211366972 C,-3.4244367965,0.6321110864,3.9885880072 C,-2.4510615985,-1.3049638453,2.9311145673 H,-1.1049917402,-0.9314118412,1.3039735232 H,-2.836310641,2.5329041781,3.1765461604 H,-4.0883243347,1.0706146058,4.7268246558 H,-2.3667826617,-2.3832092516,2.8362835587 H,-3.8521555577,-1.3996285357,4.5643321848 251 TS-E,Z[1,1]MeOH (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,Z- diimine 1 complex in MeOH) cydiimph2_EZ_b2cat2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1175902 Zero-point correction= 0.571909 (Hartree/Particle) Thermal correction to Energy= 0.602537 Thermal correction to Enthalpy= 0.603481 Thermal correction to Gibbs Free Energy= 0.511737 Sum of electronic and ZPE= -1696.545681 Sum of electronic and thermal Energies= -1696.515053 Sum of electronic and thermal Enthalpies= -1696.514109 Sum of electronic and thermal Free Energies= -1696.605854 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.098 127.740 193.093 H,-1.3152231982,-1.8397423458,-3.4496683989 C,-1.1331851885,-2.3321189577,-2.4894888725 C,-1.9312758258,-4.1705781234,-0.9226464968 C,-1.1733034966,-2.0222835379,0.0170314351 C,-2.1874950343,-3.1485994906,0.1951175287 C,-1.4037634616,-1.3475589031,-1.3559166666 C,-2.0693075811,-3.5355986828,-2.3110566003 H,-0.9222542191,-4.5872252413,-0.8090352556 H,-0.1881531128,-2.4970225576,0.0062107396 H,-3.2105512007,-2.7762114855,0.1058399354 H,-2.4623796748,-1.0732911826,-1.4009675738 H,-3.1075141057,-3.2087043765,-2.4535474948 H,-0.0915777762,-2.6603421588,-2.467585366 H,-2.6357793176,-5.0013622532,-0.8201940096 H,-2.0718382917,-3.6100935454,1.1803895921 H,-1.8582504234,-4.2778140643,-3.0866531525 N,-1.032282902,-0.9173882996,1.0114146092 N,-0.6396908761,-0.0645790034,-1.3964272648 C,-1.9598194719,-0.003316112,1.226150223 H,-1.5949792373,0.9081905797,1.6978624285 C,-1.4276367128,0.9939182755,-1.3520130538 H,-2.4739822727,0.7955278387,-1.5627876034 B,0.4063933459,-0.4838126859,1.031306682 B,0.7706893167,-0.1990772822,-0.901954556 O,1.490477775,-1.3835302326,-1.3758810733 O,1.7070093073,0.9106556785,-0.9748026854 O,1.4230191261,-1.461223685,1.4203038068 252 O,0.6962413894,0.741869911,1.7538697426 C,2.9380260902,0.3278983278,-1.0613421244 C,5.1714906977,-1.2733526416,-1.2319494336 C,4.1706607067,0.9202644564,-0.8814383281 C,2.806470396,-1.0449696836,-1.3048422582 C,3.909735466,-1.86913336,-1.40074018 C,5.2994520655,0.0881532499,-0.9746531892 H,4.254094062,1.9802899897,-0.6650995476 H,3.7983145966,-2.9329991059,-1.5819708232 H,6.2862187976,0.5180110238,-0.8346701485 H,6.0602010084,-1.8933375521,-1.2947640596 C,1.9922247612,0.6055361493,2.1644417612 C,4.5850348899,-0.1145511236,2.7523978554 C,2.8339642443,1.5775375258,2.6639774862 C,2.4255339303,-0.7116422521,1.9608535441 C,3.7213371944,-1.0972904426,2.2406698039 C,4.152010157,1.191556141,2.9610256019 H,2.4885793508,2.5963854005,2.8063737701 H,4.0527087896,-2.1140852312,2.0574004568 H,4.8439879646,1.9309209033,3.3513556577 H,5.6121674342,-0.3817733789,2.9800411103 C,-3.4255901239,-0.1543907234,1.1580404487 C,-6.2232805431,-0.2914701931,1.2467040346 C,-4.0658719779,-1.2250343097,1.7974343001 C,-4.2076432693,0.8759147344,0.6140780287 C,-5.5949827487,0.8001840209,0.6471759486 C,-5.4558347116,-1.2960408525,1.8311328556 H,-3.471832645,-1.986142675,2.2929653223 H,-3.7209922579,1.7361106169,0.1616637672 H,-6.1871872862,1.5968520166,0.2081591957 H,-5.9373810915,-2.1322525223,2.3281801125 H,-7.3069294542,-0.3485134753,1.2736584148 C,-1.0885212035,2.422712602,-1.2963691449 C,-0.7194398348,5.2026892428,-1.2692117112 C,-1.8568469616,3.2586472431,-2.1253448674 C,-0.162518133,3.0059000108,-0.4189853706 C,0.0175433378,4.3851950102,-0.4136322783 C,-1.6627695739,4.6347588118,-2.1237769148 H,-2.6006042007,2.8161924291,-2.782866395 H,0.3939170732,2.3855541527,0.2712921411 H,0.7334589723,4.8249561004,0.2740828082 H,-2.2531508681,5.2629799088,-2.7832988323 H,-0.5704196107,6.277942629,-1.2584762777 253 TS-Z,E[1,1]MeOH (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,E- diimine 1 complex in MeOH) cydiimph2_ZE_b2cat2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.132178 Zero-point correction= 0.571485 (Hartree/Particle) Thermal correction to Energy= 0.602250 Thermal correction to Enthalpy= 0.603194 Thermal correction to Gibbs Free Energy= 0.510825 Sum of electronic and ZPE= -1696.560693 Sum of electronic and thermal Energies= -1696.529928 Sum of electronic and thermal Enthalpies= -1696.528984 Sum of electronic and thermal Free Energies= -1696.621353 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.918 127.891 194.408 H,-1.5463130803,-4.0548413641,-0.2076268779 C,-1.1645260668,-3.5521752251,0.6866796203 C,-1.5208563312,-3.2160405012,3.1878303328 C,-0.7411816236,-1.3286680016,1.7888236697 C,-1.5871079458,-1.6926557148,3.0026931151 C,-1.3120806166,-2.0423144904,0.5423564391 C,-1.9575408582,-3.9781083452,1.9300916267 H,-0.4889793365,-3.4951279932,3.4369649492 H,0.2784237114,-1.6819855162,1.9680448074 H,-2.6271523704,-1.377013025,2.8565644537 H,-2.3766776483,-1.8079369064,0.499324107 H,-3.0244272512,-3.7925380915,1.747107879 H,-0.1067966786,-3.8149699386,0.7941478692 H,-2.1450864982,-3.5104260317,4.036756616 H,-1.2019165846,-1.1782772869,3.8883787364 H,-1.8432830958,-5.0546166064,2.0881778668 N,-0.6182217551,0.1112215056,1.4748993804 N,-0.6800429867,-1.4281730126,-0.6455890305 C,-1.7478384816,0.747941007,1.1850701649 H,-2.6637207819,0.161621833,1.1688676309 C,-1.3994708818,-0.707813371,-1.4836491612 H,-0.8169892146,-0.0851655449,-2.1606762343 B,0.6913353604,0.4224076685,0.81047563 B,0.7763837623,-1.1364746512,-0.5097664416 O,1.6313295808,-2.1560359472,0.0669550181 O,1.4622547972,-0.5765042373,-1.6522102679 O,1.933240446,0.2850957584,1.5453461169 254 O,0.791769583,1.5840230311,-0.0335280116 C,2.7572072523,-0.9937007519,-1.5221126098 C,5.2052900527,-2.0485458946,-0.836267311 C,3.8640466763,-0.5576305617,-2.2206199895 C,2.8579899026,-1.935390825,-0.490428241 C,4.072494286,-2.4808470845,-0.1267664527 C,5.1041614589,-1.1083667213,-1.8577184004 H,3.7722865556,0.1880540316,-3.0033801026 H,4.1420893548,-3.2027090341,0.6800054791 H,5.99870279,-0.786526464,-2.381345014 H,6.1776248512,-2.4536101962,-0.5747644585 C,2.1197382877,1.8977753253,-0.0391186927 C,4.8542003144,2.1090496233,0.2279162922 C,2.7792069242,2.8000484674,-0.8489991914 C,2.8050068871,1.1161010187,0.9005114384 C,4.1751300293,1.1948391921,1.0498383162 C,4.1721519572,2.8946977496,-0.6975130289 H,2.239121729,3.3945574471,-1.5781764644 H,4.696424973,0.5658841602,1.7638408856 H,4.7251480168,3.5896097156,-1.321385976 H,5.9325358221,2.1969480542,0.314659777 C,-1.9042246209,2.1785040702,1.0242539654 C,-2.3760180433,4.9278922158,0.7211124101 C,-0.9610174957,3.1198914973,1.4797545696 C,-3.1034175195,2.6443850545,0.451960095 C,-3.3307435772,4.0049813406,0.2922632002 C,-1.2000133,4.4792306906,1.3244736741 H,-0.0602102707,2.7837991422,1.9828233447 H,-3.8517659436,1.9236098578,0.132543443 H,-4.2562149908,4.3477116686,-0.1601016929 H,-0.4687254083,5.195580857,1.6861426281 H,-2.5551083333,5.9920344781,0.6030838755 C,-2.8422682658,-0.7025475262,-1.704109222 C,-5.5800181615,-0.5296883737,-2.292370901 C,-3.3866435515,0.4719489755,-2.2556575093 C,-3.6867936605,-1.8092161997,-1.5017113001 C,-5.0438407391,-1.7141540095,-1.7881195026 C,-4.7441027994,0.5606417728,-2.534908168 H,-2.7330275779,1.3194430153,-2.445115019 H,-3.2792554611,-2.7551863313,-1.1592706089 H,-5.6835446342,-2.5767420781,-1.6305025266 H,-5.1501087543,1.4800025097,-2.9451322994 H,-6.6404371657,-0.4634838801,-2.5140877159 255 TS-Z,Z[1,1]MeOH (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,Z- diimine 1 complex in MeOH) cydiimph2_ZZ_b2cat2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1177778 Zero-point correction= 0.572004 (Hartree/Particle) Thermal correction to Energy= 0.602692 Thermal correction to Enthalpy= 0.603636 Thermal correction to Gibbs Free Energy= 0.511405 Sum of electronic and ZPE= -1696.545773 Sum of electronic and thermal Energies= -1696.515086 Sum of electronic and thermal Enthalpies= -1696.514142 Sum of electronic and thermal Free Energies= -1696.606373 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.195 127.869 194.117 H,-1.4386497862,-2.7290910754,-2.2346679996 C,-1.0302274446,-2.8312354984,-1.2237210343 C,-1.3151312349,-3.9711396735,1.0226578153 C,-0.5989331101,-1.6089863136,0.9498943462 C,-1.4659674374,-2.6081469834,1.7110042088 C,-1.1177453973,-1.4892719268,-0.5004209336 C,-1.791428342,-3.8986032407,-0.431409084 H,-0.2649050074,-4.2886664535,1.0534409413 H,0.4070294618,-2.0386958586,0.9303973788 H,-2.5194940785,-2.3275819489,1.6688468261 H,-2.1592673189,-1.1748021361,-0.415853843 H,-2.863664767,-3.6618585354,-0.4442511549 H,0.0226003585,-3.115866027,-1.3205011189 H,-1.8952360884,-4.719328198,1.5709613639 H,-1.1586593206,-2.6544453862,2.7603479648 H,-1.671879423,-4.8696652045,-0.9211200486 N,-0.3849158917,-0.2124924492,1.4413050071 N,-0.3743372594,-0.3987106721,-1.1734142685 C,-1.3196617531,0.7324374093,1.4839505252 H,-0.9221439543,1.7434460189,1.5187543817 C,-1.007444251,0.6978130252,-1.5751601151 H,-0.3446787339,1.5233120797,-1.826331655 B,0.9966161075,0.2177337749,1.101051784 B,1.0728348989,-0.3382222623,-0.8907040465 O,1.8437337786,-1.5638068596,-0.9421035054 O,1.8609390015,0.7148672749,-1.4893471051 O,2.1412498827,-0.496279537,1.6301421713 256 O,1.2853249218,1.6281279072,1.1456834062 C,3.1259311757,0.2004305024,-1.5660427511 C,5.4731971738,-1.2366344812,-1.50165474 C,4.2975163839,0.8685068481,-1.85605927 C,3.1141004014,-1.1608232588,-1.2358595641 C,4.2755504445,-1.905511549,-1.1990828371 C,5.484828225,0.1185619658,-1.8195697673 H,4.2935327881,1.9283762585,-2.0878056077 H,4.2567478401,-2.9573903195,-0.9345799988 H,6.4272796386,0.6106939005,-2.0376292336 H,6.4065575302,-1.7899890676,-1.4783734157 C,2.6351833226,1.7006394251,1.351469057 C,5.337310782,1.3366933956,1.7415390983 C,3.4538349887,2.8077872482,1.2624921251 C,3.1463983046,0.4283819498,1.6371611847 C,4.4966588786,0.2156601486,1.8310152536 C,4.8283413421,2.6030989178,1.4660610768 H,3.0473121177,3.7867467413,1.0318961081 H,4.8828478853,-0.7784908373,2.0298778786 H,5.503935509,3.4497873264,1.3988516282 H,6.4055241401,1.2076564472,1.8843372106 C,-2.7686543794,0.6294091153,1.6582191535 C,-5.5561703884,0.665680478,2.0136541779 C,-3.3895051985,-0.2670565813,2.5440294785 C,-3.564423064,1.6050020901,1.0321886555 C,-4.9449997128,1.6095491686,1.1887110403 C,-4.7704861459,-0.2530911112,2.7088413538 H,-2.7853430394,-0.9349032262,3.1460169576 H,-3.0854844815,2.3601383979,0.4188075769 H,-5.5415696989,2.3581700575,0.6760153525 H,-5.2322200504,-0.9503525074,3.4010800987 H,-6.6340344496,0.6681669307,2.1422325878 C,-2.4060971876,0.9097341142,-1.9088118334 C,-5.0543079331,1.6011012816,-2.5930392505 C,-2.7899858329,2.2559685919,-2.0883248892 C,-3.3754793623,-0.0859314952,-2.1458002102 C,-4.6824465306,0.2638704401,-2.4687327238 C,-4.0932456343,2.5978847084,-2.4170543406 H,-2.0469796765,3.0363796336,-1.9446294687 H,-3.112595193,-1.1371402619,-2.1272756122 H,-5.4116517968,-0.5211850014,-2.6429789106 H,-4.3608019811,3.6432076799,-2.5361355815 H,-6.0764769467,1.8632956851,-2.8468182562 257 TS-E,E[1,2]MeOH (Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,E- diimine 1 complex in MeOH) cydiimph2_EE_b2cat2_1-2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1355814 Zero-point correction= 0.571644 (Hartree/Particle) Thermal correction to Energy= 0.602116 Thermal correction to Enthalpy= 0.603060 Thermal correction to Gibbs Free Energy= 0.511992 Sum of electronic and ZPE= -1696.563937 Sum of electronic and thermal Energies= -1696.533465 Sum of electronic and thermal Enthalpies= -1696.532521 Sum of electronic and thermal Free Energies= -1696.623590 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.833 127.867 191.669 H,2.0265818374,2.5297136464,3.2792958968 C,2.2437074426,2.6546290891,2.2139503174 C,2.7600978885,4.3758613213,0.3958922719 C,1.3252604094,2.4360235336,-0.1245411396 C,1.5596601299,3.9064184992,-0.4426179071 C,1.0193918474,2.2875654103,1.3837582277 C,2.5697313408,4.1241067128,1.8986204194 H,3.6554579839,3.84100205,0.0536026244 H,2.2462625247,1.8963638642,-0.355061784 H,0.67384783,4.5042737229,-0.1966548014 H,0.2495774022,3.0208498826,1.6417252662 H,1.7515655253,4.7559031039,2.2683147548 H,3.0912800888,2.013689027,1.9596008504 H,2.9385630543,5.4408515482,0.2191788428 H,1.7638945945,4.0312582501,-1.5104155702 H,3.4722138089,4.4231063919,2.4403034844 N,0.2463729288,1.7334088049,-0.8432822068 N,0.3873106901,0.9592180326,1.588909673 C,-0.9869320695,2.2086854946,-0.6181952892 H,-1.0536197552,3.1280101431,-0.0440783365 C,-0.9344477461,1.0232030944,1.7649135826 H,-1.3658197261,1.997404234,1.9642612474 B,0.5166483438,0.2745525219,-0.9787904735 B,1.1012477325,-0.1870679108,0.974662937 O,2.5195230068,-0.0551760943,0.9769119642 O,1.6729818057,-0.1077062633,-1.7213465912 O,0.6886593984,-1.5331338219,1.135510004 258 O,-0.6611337532,-0.4967150241,-1.1176988105 C,2.7441091002,-0.8348267507,-1.2909565292 C,5.0393584868,-2.2396508472,-0.5326615208 C,3.4562595803,-1.5775575406,-2.2291138566 C,3.1841828654,-0.8030451163,0.0427486553 C,4.3260157914,-1.5054856891,0.4123007129 C,4.6003713667,-2.2777622236,-1.8538709646 H,3.0989317537,-1.5847507471,-3.2542512795 H,4.6407836088,-1.4588184757,1.4503941593 H,5.1457750265,-2.8501730779,-2.5972229304 H,5.9305021736,-2.7814020519,-0.2331616412 C,-0.7467211105,-1.8126908019,-0.7879777898 C,-1.1104161373,-4.472059772,-0.0359606881 C,-1.5667771669,-2.6468715511,-1.5415319087 C,-0.1065244949,-2.3079418185,0.3563468216 C,-0.2910552009,-3.639226815,0.7219401896 C,-1.7513655853,-3.9760210624,-1.1692451586 H,-2.0624541422,-2.2242203967,-2.4105769511 H,0.211439011,-3.9982312998,1.6150604186 H,-2.3946367139,-4.6174077436,-1.7627381639 H,-1.2471031061,-5.5060042011,0.2639981078 C,-2.1724470324,1.8962589224,-1.4100793317 C,-4.5163059428,1.472955333,-2.9000598909 C,-3.4176152362,2.3528185815,-0.9415509666 C,-2.1197966595,1.2561214238,-2.6592681188 C,-3.2841177358,1.0454822307,-3.3915497696 C,-4.5775500272,2.1358232797,-1.6728249898 H,-3.4643121311,2.8681953454,0.015130022 H,-1.1629904802,0.9511944073,-3.0694930316 H,-3.2258940887,0.5527703628,-4.3574073686 H,-5.5305810561,2.4865031227,-1.2889759285 H,-5.4214178477,1.304439954,-3.4750715622 C,-1.7442022355,-0.1746615797,2.0585118846 C,-3.2696637496,-2.4512149152,2.6303894008 C,-2.9268108443,-0.4281479468,1.3556993329 C,-1.3451404027,-1.061228359,3.0694486903 C,-2.1069320945,-2.188430976,3.3555111101 C,-3.6777397599,-1.5679591931,1.6331658519 H,-3.2371131831,0.2504639418,0.5664891123 H,-0.4350823404,-0.8595549158,3.6268329666 H,-1.788473547,-2.8681791401,4.1400599367 H,-4.5806014618,-1.7673220355,1.0640479884 H,-3.8557538147,-3.3396911264,2.8444985248 259 TS-E,Z[1,2]MeOH (Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,Z- diimine 1 complex in MeOH) cydiimph2_EZ_b2cat2_1-2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1278944 Zero-point correction= 0.571911 (Hartree/Particle) Thermal correction to Energy= 0.602209 Thermal correction to Enthalpy= 0.603153 Thermal correction to Gibbs Free Energy= 0.512526 Sum of electronic and ZPE= -1696.555983 Sum of electronic and thermal Energies= -1696.525686 Sum of electronic and thermal Enthalpies= -1696.524742 Sum of electronic and thermal Free Energies= -1696.615368 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.892 127.569 190.740 H,1.4013067588,-1.7052218092,3.4968961119 C,1.4005802157,-2.2032966373,2.5223516037 C,2.721786324,-3.7465264173,0.988182785 C,1.4935539947,-1.8417926955,0.0202847859 C,2.7682034533,-2.6722317905,-0.1096610489 C,1.4833070824,-1.1578889404,1.4143700925 C,2.617505384,-3.1295272774,2.3880464267 H,1.8600444176,-4.4037712662,0.8139580174 H,0.665599456,-2.5524350281,-0.0185213684 H,3.6605439053,-2.0576203112,0.0310581972 H,2.4461066938,-0.6483538287,1.526902369 H,3.5307821528,-2.5567305025,2.595638933 H,0.4773619009,-2.7799092304,2.4357252503 H,3.6189369707,-4.3694645048,0.9218895915 H,2.820848546,-3.134423121,-1.099982944 H,2.5580484033,-3.919978164,3.1423297157 N,1.1151620637,-0.7798185153,-0.9481360451 N,0.4545229015,-0.0888746922,1.3970365663 C,1.8053506969,0.3580521043,-1.038466913 H,1.2689907811,1.1612740458,-1.5348605746 C,0.9913281947,1.1142673292,1.2095349364 H,2.0555225944,1.2043726605,1.3940677725 B,-0.3776024351,-0.6843307327,-1.0376194684 B,-0.8932132168,-0.493880761,0.8725952997 O,-1.2899326763,-1.7983206389,1.3230744777 O,-1.0279434601,-1.8942997147,-1.4705846061 O,-1.9901600304,0.4194439817,0.8920104718 260 O,-0.7765201342,0.515147005,-1.7071739382 C,-2.1020664396,-2.4515885299,-0.8436549013 C,-4.2455204597,-3.7495603613,0.3946638269 C,-3.0501373041,-3.1270636024,-1.6071436825 C,-2.2326163019,-2.4229247265,0.5552328629 C,-3.3033987736,-3.0685333019,1.1638751334 C,-4.1193581112,-3.7755832519,-0.9919095163 H,-2.924957084,-3.1402866174,-2.6856137381 H,-3.3763413863,-3.0305947933,2.2466213509 H,-4.8496655828,-4.3001016085,-1.5996706001 H,-5.0750034782,-4.2528101698,0.8807436089 C,-1.8742453988,1.2482262749,-1.3873360563 C,-4.0696306089,2.8777673093,-0.8029177845 C,-2.396891853,2.1058574182,-2.3534746356 C,-2.4517274878,1.2116933257,-0.1078158732 C,-3.5505941582,2.0246083898,0.1668909327 C,-3.4875763049,2.9221721545,-2.0676688906 H,-1.9204507353,2.1190648202,-3.3291867965 H,-3.9771350866,1.9766110304,1.164461914 H,-3.8790016838,3.5851992247,-2.832414004 H,-4.9225738286,3.5054381526,-0.5656543607 C,3.2792011473,0.4974906113,-1.0173746303 C,6.0479318123,0.9048259945,-1.228686397 C,3.8820458046,1.623999173,-0.4396621852 C,4.0795244945,-0.3932494188,-1.7472579652 C,5.4537103389,-0.1955083614,-1.8426283964 C,5.2560073687,1.8191503742,-0.5362954192 H,3.2734697271,2.356233971,0.0836729278 H,3.6163485923,-1.2300900824,-2.2603951114 H,6.0575772676,-0.897092391,-2.4096832314 H,5.7074857552,2.690481669,-0.0724549076 H,7.119867444,1.0585763278,-1.3034975186 C,0.1928463955,2.3570269342,1.1937041832 C,-1.2927826984,4.7284090432,1.217673461 C,-0.7265598151,2.6074364381,2.2220715814 C,0.378108338,3.3175879695,0.193502516 C,-0.3719535029,4.4916474144,0.1998293423 C,-1.4600997704,3.7881500532,2.2346595081 H,-0.8586754516,1.8712927737,3.00935858 H,1.0953866558,3.1381492031,-0.6023101681 H,-0.2358469726,5.2199552493,-0.5935798953 H,-2.1696649882,3.971967051,3.0357002983 H,-1.877364214,5.643279168,1.2207016203 261 TS-Z,E[1,2]MeOH (Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,E- diimine 1 complex in MeOH) cydiimph2_ZE_b2cat2_1-2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.135184 Zero-point correction= 0.572331 (Hartree/Particle) Thermal correction to Energy= 0.602746 Thermal correction to Enthalpy= 0.603691 Thermal correction to Gibbs Free Energy= 0.512517 Sum of electronic and ZPE= -1696.562853 Sum of electronic and thermal Energies= -1696.532438 Sum of electronic and thermal Enthalpies= -1696.531493 Sum of electronic and thermal Free Energies= -1696.622667 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.229 127.481 191.892 H,0.8494244632,-4.0141819632,1.2067190575 C,0.4718048641,-3.6891208425,0.2317959578 C,0.6704365601,-4.0476626636,-2.2893501751 C,0.2916541191,-1.7776320947,-1.3937692939 C,0.9743504323,-2.5570567897,-2.5098678655 C,0.8686515211,-2.2430125918,-0.0333827302 C,1.0828036562,-4.53741465,-0.8941661657 H,-0.4076015705,-4.2068095326,-2.4206390058 H,-0.7740946853,-2.0111081897,-1.4245723109 H,2.0579540986,-2.3869821149,-2.495550839 H,1.9543702216,-2.215354864,-0.1296744996 H,2.1770054598,-4.499708201,-0.8072857393 H,-0.6179273773,-3.7880236645,0.2427671763 H,1.1759428886,-4.6434401782,-3.0553007873 H,0.5947720292,-2.2268235619,-3.4816674124 H,0.7893534421,-5.583838676,-0.7677999991 N,0.3861945513,-0.3029775976,-1.4326307807 N,0.5046289325,-1.2118017159,0.9637523994 C,1.6206425743,0.1937533104,-1.3341108134 H,2.4338176357,-0.5265049333,-1.2965264932 C,1.4649540764,-0.3857917912,1.3750145939 H,1.1034304937,0.5412745255,1.8134950393 B,-0.824339571,0.3363087974,-0.8445737512 B,-0.8895193931,-0.7194512328,0.9340331561 O,-1.8828293844,-1.7224249347,0.7032457242 O,-2.0641643475,0.0102708627,-1.48259427 O,-1.1999174023,0.2600863865,1.9314706115 262 O,-0.6610818319,1.6653111524,-0.3606520376 C,-3.1841457311,-0.3697808874,-0.798877125 C,-5.5066667306,-1.2176666741,0.4985179741 C,-4.4269438442,0.0921524126,-1.2185723856 C,-3.1030024071,-1.2569277773,0.2868610088 C,-4.2619419608,-1.6744535598,0.9300720875 C,-5.5875291812,-0.3318524951,-0.5726761356 H,-4.4635945114,0.7815833474,-2.0565640098 H,-4.1674436229,-2.3601031936,1.7666058321 H,-6.5521082664,0.0340279463,-0.9095054603 H,-6.406813434,-1.5505843451,1.0048517915 C,-1.6405534814,2.116984935,0.4830985092 C,-3.5809727202,3.0185403847,2.2595207307 C,-2.3340743414,3.2879064456,0.2099438187 C,-1.9158263773,1.387069613,1.6490487429 C,-2.887807047,1.8390904526,2.5334781403 C,-3.3045315677,3.7434128239,1.1032028452 H,-2.0970598053,3.830584466,-0.7002309109 H,-3.0878002106,1.2572916604,3.4279680865 H,-3.8440079162,4.6602497862,0.8892986039 H,-4.3388796461,3.3664564093,2.9539884669 C,2.0193006336,1.570147735,-1.5802369588 C,2.9709738792,4.1621112813,-2.0957506702 C,3.342478435,1.929982373,-1.2616763136 C,1.1982935145,2.5208601441,-2.2146976172 C,1.6738760098,3.803044652,-2.4625994707 C,3.8077595896,3.2159255184,-1.5030734189 H,4.0022561083,1.1859967226,-0.8237980839 H,0.2019591333,2.2445159064,-2.5401027701 H,1.0307055148,4.5247665182,-2.9569791302 H,4.8277966953,3.4779364387,-1.2392487693 H,3.3346193518,5.165993065,-2.2916342855 C,2.8851453733,-0.6580495413,1.5753726406 C,5.6312590009,-0.9656970533,2.0846320748 C,3.7176808831,0.463298965,1.7501441384 C,3.448064462,-1.9398697973,1.7168505599 C,4.8093376517,-2.0850471326,1.9603875268 C,5.0768931221,0.3109506404,1.9897987077 H,3.2832798869,1.4574801073,1.6857822183 H,2.8202772002,-2.8244127299,1.6782511387 H,5.2270112793,-3.0809064054,2.0706422428 H,5.7036043331,1.1892508177,2.1095651048 H,6.6925851985,-1.0874379972,2.2763629186 263 TS-Z,Z[1,2]MeOH (Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,Z- diimine 1 complex in MeOH) cydiimph2_ZZ_b2cat2_1-2_ts_meoh M062X/6-31G(d,p) E(RM062X) = -1697.1213537 Zero-point correction= 0.572175 (Hartree/Particle) Thermal correction to Energy= 0.602712 Thermal correction to Enthalpy= 0.603656 Thermal correction to Gibbs Free Energy= 0.511220 Sum of electronic and ZPE= -1696.549179 Sum of electronic and thermal Energies= -1696.518642 Sum of electronic and thermal Enthalpies= -1696.517698 Sum of electronic and thermal Free Energies= -1696.610133 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.207 127.664 194.547 H,-1.1473812978,-1.7249105353,-3.1626179394 C,-0.769871386,-2.1819311148,-2.241740714 C,-1.0895788008,-4.0778228472,-0.5880489689 C,-0.4513855606,-1.8436546073,0.2475578874 C,-1.2997517534,-3.07510178,0.5556639867 C,-0.9520383846,-1.213957155,-1.0773076742 C,-1.5185413199,-3.4828370314,-1.9329815749 H,-0.0313531257,-4.3659287128,-0.6340360936 H,0.5632814454,-2.2141215986,0.0948091059 H,-2.3619463099,-2.8258477357,0.6018554372 H,-2.0167166152,-1.0304808617,-0.9239246274 H,-2.5975849217,-3.2798790116,-1.9064576218 H,0.2955813819,-2.3844572205,-2.3852802609 H,-1.6622832342,-4.9867376808,-0.3805011439 H,-1.0029695562,-3.5105506962,1.5147973262 H,-1.3482064066,-4.2034127689,-2.7385700203 N,-0.2819540964,-0.7058831398,1.204953277 N,-0.301026783,0.1067280563,-1.2272375593 C,-1.2690607343,0.1417938478,1.5135924882 H,-0.9307497719,1.1062486676,1.8800656805 C,-1.0587729722,1.1916014617,-1.0341450359 H,-0.4907076709,2.0959695513,-0.8325245601 B,1.0861933845,-0.1474281488,1.0716776612 B,1.1440701467,0.1841447769,-0.9597196181 O,1.9175570483,-0.908308282,-1.4653065344 O,2.1549278721,-1.0750384135,1.2962205808 O,1.7214029664,1.4893479129,-1.0926944496 264 O,1.2420984483,1.1644978688,1.610703754 C,3.2660135788,-1.1379805258,0.5042591261 C,5.5332336038,-1.3860977593,-1.1029288221 C,4.5155217352,-1.3176191072,1.0865846985 C,3.1513471596,-1.0742388347,-0.8927840926 C,4.2825161798,-1.196069431,-1.6899858638 C,5.6487104617,-1.4431393932,0.2835288289 H,4.5795599445,-1.359935211,2.1695961979 H,4.1626543269,-1.142271841,-2.7677424371 H,6.6199497314,-1.5843266449,0.7466736453 H,6.4128006687,-1.4831190425,-1.730944644 C,2.3540942126,1.8511844651,1.1986212556 C,4.5779398321,3.2796618981,0.3262961642 C,3.2242787207,2.4103502471,2.1249097641 C,2.5948320679,2.0017085135,-0.1767167378 C,3.7085633755,2.7139291474,-0.6063898941 C,4.3366092986,3.1308978286,1.6892849667 H,3.0128335711,2.274762366,3.1811245069 H,3.8777163573,2.8150316037,-1.674021643 H,5.0125110512,3.5680596825,2.4169240117 H,5.4444850225,3.8346428855,-0.0184428851 C,-2.6810450258,-0.1623117281,1.7659967753 C,-5.3931861485,-0.5631668127,2.3877807416 C,-3.6235107731,0.8627903428,1.5817294597 C,-3.1111737243,-1.3599495681,2.3606549261 C,-4.455584524,-1.5592569338,2.6570643444 C,-4.9679045562,0.6581334865,1.8663839832 H,-3.2891860991,1.8272825704,1.2194490487 H,-2.3847225099,-2.1146474133,2.6375274803 H,-4.7676155602,-2.4906899803,3.1193611053 H,-5.6808638601,1.4585273939,1.6926135539 H,-6.4421053614,-0.7252631239,2.6155721365 C,-2.4496900482,1.4224797035,-1.4094643951 C,-5.0952967266,2.1542748439,-2.0601534583 C,-2.9758416887,2.6766954292,-1.0393086091 C,-3.2690125749,0.56762437,-2.1718507084 C,-4.5769816911,0.9305102674,-2.4779316886 C,-4.2793081514,3.0356023464,-1.3503267306 H,-2.3446394097,3.3658569027,-0.4835213676 H,-2.8870335733,-0.3655266593,-2.5698077431 H,-5.1894315049,0.2531531937,-3.0649585981 H,-4.6583326455,4.0046997056,-1.0411500045 H,-6.1166127353,2.4280840152,-2.3048311864 265 TS-E,E[1,1]DMF (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,E- diimine 1 complex in DMF) maxstep5_cydiimph2_EE_b2cat2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1277715 Zero-point correction= 0.572168 (Hartree/Particle) Thermal correction to Energy= 0.603046 Thermal correction to Enthalpy= 0.603990 Thermal correction to Gibbs Free Energy= 0.509568 Sum of electronic and ZPE= -1696.555603 Sum of electronic and thermal Energies= -1696.524726 Sum of electronic and thermal Enthalpies= -1696.523781 Sum of electronic and thermal Free Energies= -1696.618204 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.417 127.676 198.728 H,1.1996471346,4.4540917887,0.6578112196 C,1.2340651691,3.9325671381,-0.3035723216 C,0.8974645047,4.2155207142,-2.8233155797 C,0.2049877192,2.1252325355,-1.7126955535 C,-0.140749874,3.0814802182,-2.8463270105 C,0.1244939533,2.8904180166,-0.3703221779 C,0.9851540177,4.9160906737,-1.4595797069 H,1.878954627,3.7926034132,-3.0726889094 H,1.235375948,1.7894074483,-1.855878529 H,-1.1500938237,3.4893636972,-2.713616239 H,-0.8200873389,3.4414823582,-0.3622878304 H,0.0468666846,5.4535667048,-1.2708032268 H,2.213070577,3.4581475914,-0.4020304549 H,0.6591268442,4.9477096196,-3.6005189585 H,-0.1125246371,2.5534607419,-3.8041910293 H,1.7821585497,5.6652717354,-1.4814827369 N,-0.6028164071,0.8871802796,-1.5919003037 N,0.0182392087,1.8796844699,0.7204809576 C,-1.8875781138,1.0554994107,-1.3468172399 H,-2.2644072711,2.0761927973,-1.3291623243 C,-1.1824398651,1.8548959191,1.2640304 H,-1.7872316183,2.7383722988,1.0769179103 B,0.2979477215,-0.2111478283,-1.0271843888 B,1.0194884488,0.7560620301,0.5691101418 O,2.3593281649,1.2087766532,0.1949226653 O,1.1883214286,-0.2037883992,1.6434595835 O,1.4629755329,-0.5396593415,-1.8410897316 266 O,-0.2756074964,-1.4588521618,-0.5801214183 C,2.5162684459,-0.4914642595,1.6760431863 C,5.2509131109,-0.7207950512,1.4077882801 C,3.1615296061,-1.4593216171,2.4192705772 C,3.2159185759,0.3554750553,0.8039047657 C,4.5855595037,0.2597186652,0.6520158182 C,4.5556417372,-1.561092389,2.271238309 H,2.608398102,-2.1114517466,3.0868447876 H,5.1187222952,0.917423474,-0.0262289242 H,5.0941133954,-2.3126510572,2.8396548225 H,6.3270924291,-0.8229852834,1.3100206151 C,0.6026878988,-2.4305846947,-0.9456522679 C,2.6411860153,-4.0279918382,-1.8836012634 C,0.5519410963,-3.7791571166,-0.6562849431 C,1.6477883203,-1.8736295317,-1.6971638477 C,2.6838684179,-2.6539311398,-2.1737757445 C,1.5995223634,-4.5790676063,-1.1434219373 H,-0.2646334698,-4.1948376095,-0.0750916347 H,3.4937100875,-2.2161667354,-2.7476606269 H,1.5943224688,-5.6437765283,-0.933254933 H,3.4399561891,-4.6683753297,-2.2440752849 C,-2.8680986823,-0.0082110484,-1.1726809398 C,-4.8123819836,-1.9772182164,-0.743703369 C,-3.9928848434,0.2587798749,-0.3729331569 C,-2.7523706329,-1.2647881928,-1.7870922445 C,-3.7202603026,-2.239529638,-1.5702526902 C,-4.9510528969,-0.7213880005,-0.1503361732 H,-4.0913990942,1.2365848823,0.0922860779 H,-1.9169295459,-1.4632090919,-2.4497019267 H,-3.6240750458,-3.20717721,-2.0527715138 H,-5.8040861092,-0.5083490963,0.4861904921 H,-5.5605240938,-2.7449330284,-0.5723744823 C,-1.8290915152,0.8874833948,2.147757973 C,-3.423503934,-0.8058721452,3.7176228535 C,-1.6417883642,-0.5035355844,2.1049520056 C,-2.8518603987,1.4084010425,2.9628476491 C,-3.6297379825,0.5731867095,3.7533241561 C,-2.4373625966,-1.3351735298,2.8869660057 H,-0.9053576568,-0.9383441341,1.4439954198 H,-3.0298284775,2.4805700933,2.970211201 H,-4.4042267976,0.9954656086,4.3855158445 H,-2.2919624613,-2.4098811301,2.8354085588 H,-4.0387369632,-1.464774743,4.3224232977 267 TS-E,Z[1,1]DMF (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,Z- diimine 1 complex in DMF) cydiimph2_EZ_b2cat2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1158672 Zero-point correction= 0.571928 (Hartree/Particle) Thermal correction to Energy= 0.602738 Thermal correction to Enthalpy= 0.603682 Thermal correction to Gibbs Free Energy= 0.510675 Sum of electronic and ZPE= -1696.543939 Sum of electronic and thermal Energies= -1696.513129 Sum of electronic and thermal Enthalpies= -1696.512185 Sum of electronic and thermal Free Energies= -1696.605192 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.224 127.775 195.750 H,-1.3277713925,-1.8129586106,-3.4524179085 C,-1.134792785,-2.3106272828,-2.4970144106 C,-1.9105612217,-4.1624125829,-0.9350319551 C,-1.1598937893,-2.0144422952,0.0124271709 C,-2.1666577382,-3.147459152,0.1890024589 C,-1.3987914525,-1.3331649281,-1.3559392168 C,-2.0626394171,-3.520275452,-2.3188044499 H,-0.8976844062,-4.5720289448,-0.830537506 H,-0.1689321694,-2.477061165,-0.0030688023 H,-3.1921237404,-2.7804468029,0.1057162228 H,-2.4569162969,-1.0550661508,-1.3900932903 H,-3.1039049131,-3.1985954526,-2.4504125731 H,-0.0898725745,-2.6282364345,-2.4829373752 H,-2.6083073937,-4.998781376,-0.8325096939 H,-2.0450830268,-3.6125911987,1.1718861894 H,-1.8541092768,-4.2569226413,-3.1003328337 N,-1.0271849344,-0.9125112931,1.0100307149 N,-0.628195023,-0.0539547823,-1.3973349891 C,-1.9623140399,-0.0166880347,1.2487030904 H,-1.6014586264,0.8937416594,1.7253878609 C,-1.4083031175,1.0095232109,-1.3772709162 H,-2.4562393838,0.8136034596,-1.5839866307 B,0.4114653387,-0.4624606907,1.0266733854 B,0.7831753565,-0.2050335323,-0.8977180166 O,1.4756248172,-1.4079823074,-1.3628129569 O,1.7390926599,0.8843463318,-0.9911684758 O,1.428855568,-1.4245565358,1.4386804485 268 O,0.676778102,0.7748512582,1.7392913047 C,2.9536253812,0.2804454624,-1.0858396593 C,5.1581158263,-1.3617181126,-1.2887974222 C,4.2015647952,0.8519703828,-0.9437921023 C,2.792888474,-1.0953375115,-1.3096808159 C,3.8819530803,-1.9372728883,-1.420125562 C,5.3150177898,0.0002861546,-1.0530159156 H,4.3094569332,1.913358925,-0.746060266 H,3.7502226212,-3.0009260914,-1.5883512619 H,6.3117309193,0.4157260668,-0.9434097702 H,6.0343419847,-1.997773607,-1.3653188514 C,1.962634635,0.6537740131,2.1712132093 C,4.548428532,-0.0435119976,2.8268650312 C,2.7864491224,1.6333492006,2.6866955808 C,2.4105431103,-0.6641262369,1.9854546649 C,3.7035295768,-1.0350576123,2.2993480507 C,4.1007729959,1.2599150944,3.018084049 H,2.4306039416,2.6501340028,2.8177821004 H,4.0477515933,-2.0502865045,2.1321507584 H,4.7769003101,2.0067467666,3.4217684544 H,5.5714868772,-0.3021613021,3.0811468407 C,-3.4273370002,-0.1733167355,1.1683337135 C,-6.2248086625,-0.3224700352,1.2322651611 C,-4.0684189763,-1.24711909,1.801474375 C,-4.2086369358,0.8529297276,0.615979652 C,-5.5960607786,0.7711041079,0.6367532536 C,-5.4583091049,-1.3239300345,1.8234813179 H,-3.4745029962,-2.0068331384,2.2993562675 H,-3.7206565044,1.7132736899,0.1654100052 H,-6.187879394,1.5642933874,0.1912011455 H,-5.94072612,-2.1622443229,2.3158883129 H,-7.3083077139,-0.383981714,1.2500183461 C,-1.0708564649,2.4359313392,-1.3072491763 C,-0.7150050814,5.2180190725,-1.2348730825 C,-1.8867678083,3.2874971127,-2.0739159218 C,-0.1002840104,3.0044714224,-0.4677405639 C,0.0713232036,4.3846467997,-0.4404289856 C,-1.7006616332,4.664225453,-2.0504389662 H,-2.6633077041,2.8557469883,-2.6999643364 H,0.4978611226,2.3726085934,0.1753158139 H,0.8212021055,4.8133265957,0.2175354858 H,-2.3292332382,5.3037687298,-2.6618865169 H,-0.5709775573,6.2935608228,-1.2064961196 269 TS-Z,E[1,1]DMF (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,E- diimine 1 complex in DMF) freq_cydiimph2_ZE_b2cat2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1299319 Zero-point correction= 0.571399 (Hartree/Particle) Thermal correction to Energy= 0.602269 Thermal correction to Enthalpy= 0.603213 Thermal correction to Gibbs Free Energy= 0.510272 Sum of electronic and ZPE= -1696.558533 Sum of electronic and thermal Energies= -1696.527663 Sum of electronic and thermal Enthalpies= -1696.526719 Sum of electronic and thermal Free Energies= -1696.619659 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.930 127.957 195.611 H,-1.559449,-4.044194,-0.215398 C,-1.170341,-3.545179,0.677843 C,-1.50287,-3.219551,3.182731 C,-0.736966,-1.325844,1.783706 C,-1.572691,-1.695865,3.002872 C,-1.316447,-2.034286,0.539181 C,-1.952104,-3.976324,1.926241 H,-0.46802,-3.498488,3.419304 H,0.285864,-1.676993,1.948827 H,-2.614527,-1.382599,2.864757 H,-2.380275,-1.793985,0.499824 H,-3.020407,-3.788521,1.754368 H,-0.110537,-3.803912,0.773246 H,-2.117616,-3.517871,4.037087 H,-1.182793,-1.182686,3.887194 H,-1.837569,-5.053553,2.078761 N,-0.619716,0.115163,1.474762 N,-0.681623,-1.42802,-0.649579 C,-1.750361,0.754865,1.209959 H,-2.667182,0.169078,1.193348 C,-1.392954,-0.74548,-1.518754 H,-0.80475,-0.14837,-2.2133 B,0.692773,0.424388,0.799249 B,0.778275,-1.122373,-0.50139 O,1.622366,-2.155374,0.070196 O,1.463887,-0.577151,-1.650566 O,1.931063,0.296184,1.542602 270 O,0.78572,1.596629,-0.030645 C,2.750894,-0.998634,-1.517614 C,5.194683,-2.073309,-0.834734 C,3.862264,-0.572088,-2.215634 C,2.845758,-1.941895,-0.482454 C,4.058285,-2.496364,-0.123765 C,5.099881,-1.132145,-1.855224 H,3.776548,0.17476,-2.997998 H,4.125494,-3.219336,0.682225 H,5.996116,-0.816568,-2.379816 H,6.163928,-2.486648,-0.574483 C,2.107953,1.910882,-0.037328 C,4.844527,2.133236,0.235224 C,2.767273,2.821599,-0.838571 C,2.796399,1.125502,0.901758 C,4.166899,1.211566,1.0512 C,4.160576,2.921646,-0.685829 H,2.227075,3.419891,-1.564582 H,4.691445,0.581898,1.762209 H,4.711132,3.622868,-1.304866 H,5.92246,2.224669,0.32392 C,-1.904185,2.184982,1.042801 C,-2.367605,4.93417,0.728055 C,-0.958077,3.124963,1.49355 C,-3.100807,2.651709,0.466411 C,-3.324404,4.012423,0.301083 C,-1.192838,4.48439,1.333364 H,-0.058341,2.78631,1.996125 H,-3.849201,1.931203,0.146195 H,-4.247812,4.356059,-0.154584 H,-0.459469,5.200136,1.6918 H,-2.543625,5.998298,0.606013 C,-2.838839,-0.72532,-1.728124 C,-5.579742,-0.528003,-2.291305 C,-3.374637,0.448276,-2.289112 C,-3.693921,-1.818823,-1.501799 C,-5.052604,-1.712003,-1.776606 C,-4.733993,0.54965,-2.555453 H,-2.713255,1.285621,-2.495512 H,-3.293571,-2.763636,-1.148048 H,-5.700808,-2.564509,-1.60066 H,-5.133671,1.468495,-2.972653 H,-6.64135,-0.452284,-2.503594 271 TS-Z,Z[1,1]DMF (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,Z- diimine 1 complex in DMF) maxstep1_cfc_cydiimph2_ZZ_b2cat2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1165081 Zero-point correction= 0.572293 (Hartree/Particle) Thermal correction to Energy= 0.602950 Thermal correction to Enthalpy= 0.603894 Thermal correction to Gibbs Free Energy= 0.512231 Sum of electronic and ZPE= -1696.544216 Sum of electronic and thermal Energies= -1696.513558 Sum of electronic and thermal Enthalpies= -1696.512614 Sum of electronic and thermal Free Energies= -1696.604277 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.357 127.753 192.922 H,-1.4570409996,-2.6934073669,-2.2538961766 C,-1.0425867849,-2.8090593701,-1.2467956186 C,-1.3162837939,-3.9696023064,0.9890523325 C,-0.5922618835,-1.6083543165,0.9374018783 C,-1.4573486704,-2.6134081815,1.6928229425 C,-1.1157616011,-1.4736055421,-0.5097537281 C,-1.8039301945,-3.8803000552,-0.4604004736 H,-0.2665877864,-4.2899346149,1.0072609866 H,0.416438945,-2.0311026587,0.9097222098 H,-2.5100769144,-2.3282755609,1.6613156915 H,-2.1532414793,-1.1464701949,-0.4189692276 H,-2.8748032476,-3.6373029808,-0.4619712197 H,0.0093068546,-3.0939678952,-1.3524298699 H,-1.8935308112,-4.7222548473,1.5340898604 H,-1.1438790223,-2.6719550505,2.7396970547 H,-1.6937726417,-4.8470480311,-0.9606338015 N,-0.3846057594,-0.2154531452,1.4377676208 N,-0.3595147057,-0.3922534236,-1.1807846506 C,-1.3260742714,0.7158919053,1.5143840748 H,-0.9382497494,1.7301491302,1.5591273267 C,-0.9736165561,0.6969144023,-1.6223152221 H,-0.2956357016,1.5022026173,-1.8961952783 B,0.993128121,0.2346329974,1.086562398 B,1.0890485299,-0.3478600861,-0.8855851384 O,1.833668202,-1.5895138223,-0.9204643505 O,1.8964555336,0.6792061675,-1.4975592818 O,2.1453419707,-0.4500818017,1.6328081013 272 O,1.2488552111,1.6503994147,1.123196731 C,3.14657866,0.1419847775,-1.562193682 C,5.4678102177,-1.3425433797,-1.47731017 C,4.3329042592,0.7791650193,-1.8642481314 C,3.1079935308,-1.2161833421,-1.2102031728 C,4.2561892292,-1.9814667201,-1.1634528966 C,5.505798604,0.006255826,-1.817677742 H,4.3519997406,1.834890514,-2.1135380914 H,4.2177823502,-3.0289993996,-0.8843003765 H,6.4573536629,0.4761947799,-2.0450304854 H,6.3897024648,-1.9144543981,-1.4463704418 C,2.5911075444,1.7514768343,1.3267270623 C,5.3007291618,1.4487263663,1.7407559351 C,3.3894886972,2.8736507132,1.2344160783 C,3.1277328834,0.4902575416,1.6293880514 C,4.481808989,0.3111191406,1.8347417362 C,4.7672001141,2.7009209487,1.4492998904 H,2.9653952148,3.8425785881,0.9934066773 H,4.8889342718,-0.6719355025,2.0467953204 H,5.4249380988,3.5613577878,1.3794303797 H,6.3702251418,1.343301787,1.8929949642 C,-2.775500584,0.5906239845,1.6867534814 C,-5.5598451714,0.5866223413,2.0632479599 C,-3.3742743791,-0.2998724667,2.5934486459 C,-3.5920798543,1.5354304894,1.0417165738 C,-4.9715701615,1.520694477,1.2111848384 C,-4.7539155927,-0.305986515,2.769397181 H,-2.7530990564,-0.950061451,3.1981179779 H,-3.1323574966,2.2807681516,0.4017217223 H,-5.585081464,2.2462014582,0.6856697298 H,-5.1987841602,-0.9980610053,3.4775474266 H,-6.6363429127,0.5748815655,2.2015925832 C,-2.3733162887,0.9354637935,-1.9336639291 C,-5.0200174365,1.6763319634,-2.5745729941 C,-2.7336649674,2.2885571296,-2.114125604 C,-3.3671511482,-0.0415669104,-2.1467074897 C,-4.672580048,0.3327907416,-2.4489848719 C,-4.0357817333,2.6546274435,-2.4202489057 H,-1.9728512422,3.0545091341,-1.9875303417 H,-3.1248265106,-1.0975880503,-2.123426544 H,-5.4205738209,-0.4383202685,-2.6045822025 H,-4.2848820512,3.7045032702,-2.5387961869 H,-6.0410295504,1.9578884587,-2.8111741277 273 TS-E,E[1,2]DMF (Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,E- diimine 1 complex in DMF) cydiimph2_EE_b2cat2_1-2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1342279 Zero-point correction= 0.571696 (Hartree/Particle) Thermal correction to Energy= 0.602301 Thermal correction to Enthalpy= 0.603245 Thermal correction to Gibbs Free Energy= 0.510859 Sum of electronic and ZPE= -1696.562532 Sum of electronic and thermal Energies= -1696.531927 Sum of electronic and thermal Enthalpies= -1696.530983 Sum of electronic and thermal Free Energies= -1696.623369 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.950 127.899 194.443 H,2.0064834789,2.522925618,3.2817186533 C,2.231745849,2.6447265758,2.2176428425 C,2.7641086736,4.3602938772,0.3991543495 C,1.3266875099,2.423379389,-0.1258486219 C,1.5664962458,3.8930593649,-0.4443075943 C,1.0130276736,2.2757465119,1.3801500209 C,2.5634750863,4.1124922709,1.9011736313 H,3.659220788,3.8208977403,0.0634474249 H,2.2464702904,1.879625915,-0.351511957 H,0.68101549,4.4927981583,-0.2018213194 H,0.2390238119,3.0073127305,1.6314479791 H,1.7441455442,4.7471391188,2.263221194 H,3.0763861574,1.9975042049,1.9697215995 H,2.9477758328,5.4240952335,0.2210252706 H,1.7746889886,4.0167937054,-1.5114579156 H,3.4629434244,4.4111406631,2.4479720704 N,0.2496949681,1.7226693287,-0.8492323738 N,0.3866401625,0.9441250226,1.5875336577 C,-0.9815559035,2.2082020451,-0.6477969501 H,-1.0540925982,3.1240708071,-0.0685873522 C,-0.931617177,1.0044516903,1.7831520792 H,-1.3691345021,1.9843638139,1.933555098 B,0.5182675282,0.2611693688,-0.9788670448 B,1.1106285802,-0.1984963984,0.9748928831 O,2.5253464829,-0.0509493402,0.9771945199 O,1.6723792977,-0.1276941891,-1.7165849865 O,0.7046230046,-1.5445272232,1.1257489471 274 O,-0.66056312,-0.5043521824,-1.1067031789 C,2.7514335653,-0.8331602493,-1.2872659835 C,5.0771032592,-2.1955752922,-0.5328290378 C,3.4749793896,-1.5680869681,-2.2241769433 C,3.1971709154,-0.7894188036,0.0460910286 C,4.3537130939,-1.4703884579,0.4116911356 C,4.6330039794,-2.2469759855,-1.8518271329 H,3.1149193567,-1.5857451907,-3.2480531697 H,4.6724204273,-1.4145886386,1.4479512815 H,5.1851671768,-2.8122158209,-2.5956479807 H,5.9790277282,-2.7198843118,-0.2346091744 C,-0.7358602187,-1.8204214969,-0.7903299441 C,-1.0412685005,-4.50003328,-0.07887687 C,-1.5466294649,-2.6594799527,-1.5497142143 C,-0.0767655923,-2.3218254905,0.3418090761 C,-0.2333481173,-3.6629079252,0.686769172 C,-1.7023993404,-3.9980359318,-1.1980809933 H,-2.0549152107,-2.2334369311,-2.4095771712 H,0.2824730918,-4.0266523473,1.5700321469 H,-2.3377299736,-4.6422608123,-1.7969847529 H,-1.1545195083,-5.5414125784,0.2045624221 C,-2.1663668913,1.8836479916,-1.4315391251 C,-4.5163738177,1.4472667751,-2.9108145481 C,-3.4080783736,2.3615399704,-0.9739191065 C,-2.1211255619,1.2139564653,-2.6661114904 C,-3.2875842963,0.9982603007,-3.3928545755 C,-4.5709145046,2.1380390611,-1.6988183005 H,-3.4487865359,2.9030083023,-0.0314672963 H,-1.1678994179,0.8900025883,-3.068764574 H,-3.2345516372,0.4837049288,-4.3475214913 H,-5.5202082132,2.5062777384,-1.3224114319 H,-5.4230004239,1.2738159088,-3.4817888155 C,-1.7576081406,-0.1715814061,2.0870996882 C,-3.3755742553,-2.3808439872,2.6781602001 C,-3.0209779113,-0.3054740568,1.4960346686 C,-1.3271337423,-1.1431391002,3.003235388 C,-2.1331346105,-2.2379369657,3.2955123585 C,-3.8181984326,-1.4094237978,1.7812403773 H,-3.3617500352,0.4458151068,0.7895397371 H,-0.3612723418,-1.0312214795,3.4852048819 H,-1.7893814797,-2.983368257,4.0062138296 H,-4.7859890654,-1.5122659441,1.3002155771 H,-3.9983599366,-3.2417494993,2.9003412275 275 TS-E,Z[1,2]DMF(Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,Z- diimine 1 complex in DMF) cydiimph2_EZ_b2cat2_1-2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1266158 Zero-point correction= 0.571924 (Hartree/Particle) Thermal correction to Energy= 0.602336 Thermal correction to Enthalpy= 0.603280 Thermal correction to Gibbs Free Energy= 0.511802 Sum of electronic and ZPE= -1696.554692 Sum of electronic and thermal Energies= -1696.524280 Sum of electronic and thermal Enthalpies= -1696.523336 Sum of electronic and thermal Free Energies= -1696.614814 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 377.971 127.640 192.531 H,1.4114703804,-1.6645712809,3.4910831753 C,1.3976630099,-2.1728900116,2.5218551388 C,2.6901221415,-3.7444576921,0.9929694096 C,1.4800281181,-1.8330139955,0.0152442317 C,2.7447402674,-2.6788530139,-0.1127997708 C,1.4797123463,-1.1389616705,1.4031294258 C,2.6030785294,-3.1137404251,2.3878999048 H,1.8178578427,-4.3904873755,0.8294706929 H,0.6429109168,-2.5330886512,-0.0175375208 H,3.6442051501,-2.0735225872,0.0220321216 H,2.4439004489,-0.6289978833,1.5040740383 H,3.524380025,-2.5493162142,2.582525857 H,0.4652769214,-2.7359639259,2.4460359014 H,3.5778882641,-4.3805390017,0.926386534 H,2.7904240972,-3.147631408,-1.1003735852 H,2.5410149289,-3.896401259,3.1500023115 N,1.1107962997,-0.7718336647,-0.9576314658 N,0.4494960639,-0.0706073874,1.3863731452 C,1.8148489452,0.353506284,-1.0663967296 H,1.2817491129,1.1631399785,-1.5554682977 C,0.9804653239,1.1360694808,1.2172185452 H,2.0487174907,1.2259025132,1.3750192114 B,-0.3832874973,-0.6626126532,-1.0455657088 B,-0.9003227282,-0.4810588675,0.8672300602 O,-1.2819958959,-1.7872575875,1.3172912293 O,-1.0455807585,-1.8613164615,-1.4813752433 O,-1.9976792406,0.4280810564,0.8815665662 276 O,-0.7637213631,0.5494013594,-1.6994197612 C,-2.0949116891,-2.4430062065,-0.8468096426 C,-4.1961830403,-3.8032094275,0.4049795391 C,-3.0362546743,-3.1376544228,-1.6033210562 C,-2.2134968869,-2.4259813114,0.5554168813 C,-3.262575775,-3.1038287645,1.1683128717 C,-4.0836487309,-3.8163654251,-0.9829218716 H,-2.9219471346,-3.1418582773,-2.6829142652 H,-3.3252986516,-3.0754259952,2.2518318238 H,-4.8066027512,-4.3547100792,-1.5873927782 H,-5.0075681901,-4.3303670778,0.8962494723 C,-1.8683144022,1.2691744821,-1.389907361 C,-4.0876888114,2.8733932176,-0.8164318495 C,-2.3929672635,2.1269255043,-2.3555522974 C,-2.4577792522,1.2194623065,-0.1141502971 C,-3.5678257903,2.020547562,0.1535963864 C,-3.4950730776,2.9304250281,-2.0757593773 H,-1.9090016852,2.1505326795,-3.3271894228 H,-4.0022412599,1.9637601076,1.147044858 H,-3.886774782,3.5930476384,-2.8406968335 H,-4.9491514498,3.4909600487,-0.5834737449 C,3.288946025,0.4796413824,-1.0394357485 C,6.0629113141,0.8613006875,-1.2365735286 C,3.8983893001,1.6057034258,-0.4674107196 C,4.0865451203,-0.4243216335,-1.7562897414 C,5.4629896619,-0.2393646603,-1.844636613 C,5.274563848,1.7883398507,-0.5569475316 H,3.2917666904,2.3461144254,0.0462961167 H,3.6186899662,-1.2616440277,-2.2643865665 H,6.0643518891,-0.950901536,-2.4016967267 H,5.7307474813,2.6594607235,-0.0975299378 H,7.136480656,1.0051424568,-1.306002108 C,0.1812520261,2.3761930153,1.2133331361 C,-1.2990535999,4.7510709351,1.2531824151 C,-0.762856466,2.6064056684,2.2238733209 C,0.3927704701,3.3587370144,0.2391489434 C,-0.3534976822,4.5346720098,0.2531747664 C,-1.4936406828,3.7888327721,2.24428766 H,-0.9157709825,1.8530210322,2.9902767614 H,1.1284589405,3.1926741971,-0.5428185408 H,-0.196094869,5.2803562627,-0.5197723802 H,-2.2221338418,3.9574449281,3.0315020263 H,-1.8809765074,5.6674926777,1.2626980245 277 TS-Z,E[1,2]DMF (Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,E- diimine 1 complex in DMF) cydiimph2_ZE_b2cat2_1-2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1343495 Zero-point correction= 0.572316 (Hartree/Particle) Thermal correction to Energy= 0.602816 Thermal correction to Enthalpy= 0.603760 Thermal correction to Gibbs Free Energy= 0.512027 Sum of electronic and ZPE= -1696.562033 Sum of electronic and thermal Energies= -1696.531533 Sum of electronic and thermal Enthalpies= -1696.530589 Sum of electronic and thermal Free Energies= -1696.622322 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.273 127.562 193.069 H,0.8478852486,-4.0045121781,1.2190259868 C,0.4678941827,-3.6824159471,0.2439770544 C,0.6591746361,-4.0498329889,-2.2764331047 C,0.287889867,-1.7765378236,-1.3867090304 C,0.9672402333,-2.5607487023,-2.5015732738 C,0.8658419332,-2.2377237361,-0.0267329442 C,1.0734358816,-4.5362481256,-0.8805417567 H,-0.4197446541,-4.2056720736,-2.4042139743 H,-0.778253274,-2.0076599363,-1.4135010127 H,2.0513440652,-2.3941938416,-2.4880235368 H,1.9516638551,-2.2079113426,-0.1230258344 H,2.1679230829,-4.5004164571,-0.796882204 H,-0.6224500072,-3.7727029183,0.2600475658 H,1.1607337922,-4.6497591696,-3.0416459192 H,0.58837301,-2.2317709034,-3.4740661226 H,0.7781328154,-5.58162996,-0.7503228231 N,0.3828173156,-0.3021428433,-1.4295439072 N,0.4974368146,-1.2088351368,0.9701526971 C,1.6158405379,0.196342739,-1.348359911 H,2.4299686069,-0.5226442221,-1.30134807 C,1.4533464876,-0.3988308236,1.4124717258 H,1.0884086184,0.5183662246,1.867586344 B,-0.8328301416,0.3364540663,-0.8452904209 B,-0.8994317313,-0.7136228068,0.9333625593 O,-1.884971937,-1.7220259316,0.7018336285 O,-2.0664158585,0.0006151704,-1.4873157183 O,-1.2065439883,0.2676965625,1.9270165439 278 O,-0.6707364122,1.6670081556,-0.3725339705 C,-3.18346403,-0.3862300042,-0.8142485047 C,-5.5112378058,-1.2625094064,0.4615612764 C,-4.4297664618,0.0557042581,-1.2477001851 C,-3.1026915685,-1.2701129522,0.2769027419 C,-4.2644670143,-1.7007204382,0.9073411962 C,-5.5921669951,-0.3813808048,-0.6133055442 H,-4.467978553,0.740622162,-2.0891047782 H,-4.1707577581,-2.3836396806,1.7460394067 H,-6.557728406,-0.0299122404,-0.9624659454 H,-6.412107611,-1.6064525214,0.9591548476 C,-1.6353587168,2.1257304079,0.4773554745 C,-3.5434677455,3.0572958374,2.2781464237 C,-2.315091483,3.3081190283,0.2156526758 C,-1.9088762499,1.3981814489,1.6479019163 C,-2.8644359665,1.8672319111,2.5424705518 C,-3.2689099054,3.7786461874,1.1194331955 H,-2.0796210448,3.8495822563,-0.6955488796 H,-3.0621719316,1.2896262676,3.44000173 H,-3.7958687606,4.7041965417,0.911949029 H,-4.2875382686,3.416159717,2.9819246709 C,2.0138826473,1.5731302596,-1.5848870368 C,2.972145625,4.1668168571,-2.0840820339 C,3.3407241766,1.9262086591,-1.2720685445 C,1.1908621991,2.5338246761,-2.2018716475 C,1.6701560012,3.8158422219,-2.4424655548 C,3.8095659144,3.2124257944,-1.505486763 H,3.999789885,1.1762008837,-0.8431771611 H,0.1891633441,2.2660053873,-2.5156976521 H,1.0257360829,4.5449985208,-2.9241215606 H,4.8322999331,3.4682612773,-1.2463250554 H,3.3381680071,5.1707757746,-2.2746338931 C,2.87784342,-0.6632089729,1.5903243737 C,5.6335170027,-0.9583327835,2.0565776456 C,3.7067162825,0.4618234601,1.7607564758 C,3.4507323737,-1.9427276032,1.7140254825 C,4.8163053558,-2.0816621002,1.9362604337 C,5.0702444097,0.3157036063,1.9789309866 H,3.2659550801,1.4538174763,1.7074459816 H,2.8267893487,-2.830014361,1.6772556131 H,5.241400894,-3.0757175441,2.0326887853 H,5.6937093419,1.1967907858,2.094407798 H,6.6981968816,-1.0750410711,2.231472597 279 TS-Z,Z[1,2]DMF(Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,Z- diimine 1 complex in DMF) cydiimph2_ZZ_b2cat2_1-2_ts_dmf M062X/6-31G(d,p) E(RM062X) = -1697.1213922 Zero-point correction= 0.572434 (Hartree/Particle) Thermal correction to Energy= 0.602974 Thermal correction to Enthalpy= 0.603918 Thermal correction to Gibbs Free Energy= 0.511365 Sum of electronic and ZPE= -1696.548958 Sum of electronic and thermal Energies= -1696.518418 Sum of electronic and thermal Enthalpies= -1696.517474 Sum of electronic and thermal Free Energies= -1696.610027 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.372 127.603 194.794 H,-1.1494743682,-1.7123332388,-3.1595658557 C,-0.7679632636,-2.1723399513,-2.2417631899 C,-1.0794595254,-4.0749755634,-0.5938092985 C,-0.4419088354,-1.8429378806,0.246534591 C,-1.288443888,-3.0759779538,0.5533238211 C,-0.9459907392,-1.208462985,-1.0732925066 C,-1.5131834193,-3.4758081767,-1.9355390029 H,-0.0206322428,-4.3601550713,-0.6436952828 H,0.5730486759,-2.2100346619,0.08898868 H,-2.3506906734,-2.8273808542,0.6013548474 H,-2.009464762,-1.0213466374,-0.9149901922 H,-2.5924210449,-3.2746252773,-1.9043893944 H,0.2985284144,-2.3680500789,-2.3868708722 H,-1.6495063174,-4.9858899832,-0.388127348 H,-0.9907879447,-3.5134046351,1.511286893 H,-1.3445453583,-4.1934889757,-2.7439992936 N,-0.270663269,-0.7088073189,1.2064974455 N,-0.2899658338,0.1090080039,-1.2259769638 C,-1.255064511,0.131058068,1.534903544 H,-0.9132963404,1.0952346982,1.8984803542 C,-1.0419452937,1.2007778938,-1.065444769 H,-0.4690526421,2.1060880457,-0.885048096 B,1.1006749986,-0.1508290501,1.0750128282 B,1.1575981616,0.1834683982,-0.957842167 O,1.9213775687,-0.9130560555,-1.4637637939 O,2.1625263358,-1.0837567172,1.2953236534 O,1.7319338136,1.4873777134,-1.0892287065 280 O,1.2517371697,1.1571494086,1.6180858321 C,3.2661109235,-1.1626032286,0.5038531622 C,5.5262886792,-1.4611231742,-1.1099125725 C,4.5144027428,-1.3715356285,1.0811561938 C,3.1498719598,-1.0959500902,-0.8949745133 C,4.2780497358,-1.2431101989,-1.6932009345 C,5.6434489434,-1.5216980919,0.2761306765 H,4.5807151568,-1.4183931035,2.1636817133 H,4.1576549723,-1.18833942,-2.7707108027 H,6.6120394748,-1.6855998038,0.7373621779 H,6.4017394681,-1.5778428343,-1.7403188547 C,2.3455879375,1.8622589651,1.2050139432 C,4.5312602314,3.3558898592,0.334516363 C,3.1989585275,2.4502882795,2.1302579774 C,2.5860489304,2.0166790445,-0.1721955156 C,3.6804346389,2.7621185094,-0.598001561 C,4.2911113533,3.2027820029,1.69706487 H,2.9885864599,2.3131929978,3.1863555368 H,3.8483456149,2.8682364393,-1.6651640724 H,4.9513471715,3.6613560434,2.4258922785 H,5.3811537453,3.9362348076,-0.0098989239 C,-2.669718151,-0.167479646,1.7744894747 C,-5.3893553042,-0.5561489321,2.3729403378 C,-3.6056466479,0.8631804562,1.5855142683 C,-3.1116786609,-1.3658970381,2.3593535309 C,-4.4594461635,-1.5590824097,2.644195934 C,-4.9533010436,0.6648148955,1.8594528392 H,-3.2631894491,1.8258621969,1.225292638 H,-2.3911279147,-2.1260644113,2.6367729507 H,-4.7804755403,-2.4909970091,3.0991051308 H,-5.6607874925,1.4693128635,1.682800364 H,-6.4407456964,-0.7132065573,2.5921799585 C,-2.4381699584,1.4262429064,-1.4201951547 C,-5.0957942222,2.1498497747,-2.0366500766 C,-2.9618807149,2.6823689142,-1.0507231472 C,-3.2686383772,0.5649151389,-2.163942703 C,-4.5817761836,0.923698463,-2.4527386993 C,-4.2702526652,3.0371204938,-1.3449287078 H,-2.3239141474,3.3756586979,-0.5080874278 H,-2.8909158409,-0.3702785923,-2.5609308617 H,-5.2018763144,0.2410389474,-3.025307563 H,-4.6461959119,4.0075741611,-1.036464768 H,-6.1209111327,2.4205501483,-2.2680032164 281 TS-E,E[1,1]benzene (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,E- diimine 1 complex in benzene) cydiimph2_EE_b2cat2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1219456 Zero-point correction= 0.572217 (Hartree/Particle) Thermal correction to Energy= 0.603081 Thermal correction to Enthalpy= 0.604025 Thermal correction to Gibbs Free Energy= 0.510510 Sum of electronic and ZPE= -1696.549728 Sum of electronic and thermal Energies= -1696.518864 Sum of electronic and thermal Enthalpies= -1696.517920 Sum of electronic and thermal Free Energies= -1696.611436 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.439 127.668 196.820 H,1.2182741198,4.4347142995,0.6335524827 C,1.2556056111,3.9028106858,-0.3220247966 C,0.9321056236,4.1544126684,-2.8476209141 C,0.2352982473,2.074691325,-1.7131833505 C,-0.1012612281,3.0158433639,-2.8625206452 C,0.1506559235,2.8551193508,-0.3815990149 C,1.0122952209,4.8714894333,-1.4915369885 H,1.9157957531,3.7314188078,-3.0866442728 H,1.2651860587,1.7309216471,-1.8449995779 H,-1.1156434191,3.419119679,-2.7477115815 H,-0.7982912599,3.4016067681,-0.3844115946 H,0.0735317331,5.4139600773,-1.3160062348 H,2.23412049,3.4248731146,-0.405340993 H,0.6982405164,4.8763962783,-3.6355651203 H,-0.0653296629,2.4742172086,-3.8121862074 H,1.8075712064,5.6220118363,-1.518749725 N,-0.5772089967,0.8476074153,-1.580333441 N,0.0478487811,1.8602390502,0.7170434946 C,-1.8623881098,1.011233983,-1.3398451204 H,-2.2426094096,2.0312359661,-1.3043076026 C,-1.1417633919,1.8424947665,1.2802818453 H,-1.7540083594,2.7198942401,1.0821811405 B,0.3191605596,-0.2648872582,-1.0038641628 B,1.0556627193,0.725422831,0.581170402 O,2.3849826952,1.1833082121,0.1983996005 O,1.2135795511,-0.1833579019,1.6885714464 O,1.4522664718,-0.6159234409,-1.8391064499 282 O,-0.2946999642,-1.4861975515,-0.5591372938 C,2.5541804696,-0.3499282327,1.8510882728 C,5.308363389,-0.3614098459,1.8182192235 C,3.2083309835,-1.1780833929,2.7394845156 C,3.2548153696,0.4657862493,0.9542869724 C,4.6344814355,0.4767896382,0.9162720956 C,4.6116422406,-1.1698752294,2.7097695403 H,2.6518985433,-1.8063486351,3.4259455699 H,5.1666507934,1.1092354266,0.2143445431 H,5.1589717459,-1.8102537946,3.3937243103 H,6.3934164327,-0.3778079871,1.8148783253 C,0.4536359417,-2.4986188017,-1.0800649558 C,2.235503048,-4.1797584848,-2.3303965757 C,0.2701592837,-3.8576449046,-0.9314869217 C,1.5023473554,-1.9714422239,-1.8443112787 C,2.4121271234,-2.7954216418,-2.4772340798 C,1.1887665814,-4.7004403846,-1.5763439243 H,-0.5511647462,-4.2454838914,-0.3387348203 H,3.2258735683,-2.3800277951,-3.0609638838 H,1.0790785295,-5.7757427291,-1.48102292 H,2.9328957179,-4.8548293767,-2.8157598757 C,-2.8326591392,-0.0687241209,-1.2149897664 C,-4.7472560596,-2.0890641236,-0.9355637894 C,-3.9601288959,0.1242387325,-0.4020816271 C,-2.6898039218,-1.2820304209,-1.9052555864 C,-3.6420501665,-2.2827634457,-1.7630699242 C,-4.90703934,-0.8810237944,-0.2582089348 H,-4.0730394071,1.0604945825,0.1389562798 H,-1.8413563701,-1.4238530382,-2.5667383966 H,-3.5220066206,-3.2164096167,-2.3032814339 H,-5.7651822283,-0.7253776356,0.3874578518 H,-5.4866124563,-2.8759028185,-0.8240265968 C,-1.7600886789,0.8986570312,2.2088072232 C,-3.2585290477,-0.7452926795,3.9115808544 C,-1.5966258321,-0.4943615149,2.1689595106 C,-2.7129997465,1.4472543348,3.0864777853 C,-3.4431263073,0.6363468534,3.9429845038 C,-2.3457074675,-1.3009295959,3.0189764618 H,-0.9138237835,-0.9494602401,1.4645361103 H,-2.8675135321,2.5233050213,3.0979012191 H,-4.1603262555,1.0785331586,4.6268433656 H,-2.2189536251,-2.3776067875,2.97181918 H,-3.8350064051,-1.3863457004,4.5710882522 283 TS-E,Z[1,1]benzene (Reductive coupling transition state from dicoordinate 1,1-B2cat2-E,Z- diimine 1 complex in benzene) cydiimph2_EZ_b2cat2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1115261 Zero-point correction= 0.572532 (Hartree/Particle) Thermal correction to Energy= 0.603424 Thermal correction to Enthalpy= 0.604368 Thermal correction to Gibbs Free Energy= 0.510205 Sum of electronic and ZPE= -1696.538994 Sum of electronic and thermal Energies= -1696.508102 Sum of electronic and thermal Enthalpies= -1696.507158 Sum of electronic and thermal Free Energies= -1696.601321 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.654 127.549 198.182 H,-1.2409440466,-1.9322430581,-3.4029266878 C,-1.0435809537,-2.3879834053,-2.4276876201 C,-1.7960393989,-4.1815569238,-0.7880789397 C,-1.0645097233,-1.9870087995,0.0699011616 C,-2.0583955392,-3.1239374453,0.2949153599 C,-1.31025633,-1.3665391649,-1.3258892254 C,-1.9598162132,-3.5974550838,-2.1964131137 H,-0.7787341201,-4.5759062258,-0.6716990846 H,-0.0683709157,-2.4392454865,0.0727767103 H,-3.089375749,-2.7738073167,0.2038979295 H,-2.3726346723,-1.1002116472,-1.3630229639 H,-3.0059417384,-3.2941667108,-2.3373720783 H,0.004846267,-2.6915811008,-2.4044974131 H,-2.4828771685,-5.0216927447,-0.6492082114 H,-1.9265480188,-3.5490699741,1.2947081448 H,-1.748952704,-4.3637757316,-2.9479820834 N,-0.9410838678,-0.8435970983,1.0149928036 N,-0.5504795413,-0.0887400879,-1.4134612428 C,-1.8741864041,0.0664182328,1.2030025209 H,-1.5069793839,0.9901764643,1.6484236231 C,-1.3358401902,0.9707468375,-1.4025705773 H,-2.3834305722,0.7624134514,-1.6005939594 B,0.5143856886,-0.393279359,1.0334359589 B,0.8799508534,-0.2112046802,-0.9135686132 O,1.5485274582,-1.4366698062,-1.3333233259 O,1.7978695195,0.878397997,-1.1411971643 O,1.4800684557,-1.3661307803,1.5114380562 284 O,0.7453164628,0.8476606008,1.741478886 C,2.9714681169,0.3088108058,-1.5271056792 C,5.1024639353,-1.26653076,-2.2788000409 C,4.1746776948,0.9303644495,-1.7896256668 C,2.8223597607,-1.0791921212,-1.6350729982 C,3.8747794427,-1.8907459779,-2.0077668879 C,5.2490629576,0.1122765247,-2.1728794014 H,4.2758776664,2.0060128939,-1.6984525463 H,3.7489734113,-2.9651392644,-2.0839373307 H,6.2108421679,0.5675248734,-2.3855027858 H,5.9511754156,-1.8749740077,-2.5739812528 C,1.8612839127,0.6389763935,2.4969327027 C,4.0936103277,-0.2392580158,3.8461417283 C,2.5248150056,1.5397585781,3.3032875806 C,2.2956492353,-0.6856551345,2.3556853916 C,3.4142044833,-1.1479587867,3.0205225451 C,3.6599546621,1.0747072813,3.9855067914 H,2.1756761326,2.5619782081,3.4001407383 H,3.7469536057,-2.1727385934,2.8998654599 H,4.2074434839,1.7557266425,4.6287844418 H,4.9763981478,-0.5717144845,4.3825993597 C,-3.3408241215,-0.083623602,1.1241955942 C,-6.1414041642,-0.2132016609,1.1783505762 C,-3.9941593041,-1.1381922305,1.7761232088 C,-4.1153228091,0.9382927077,0.5539210314 C,-5.5026044992,0.8663896307,0.569816038 C,-5.3841062836,-1.2070898015,1.7917129532 H,-3.4072390308,-1.8870590742,2.2975901866 H,-3.6187487629,1.7911468655,0.0980355479 H,-6.0871437383,1.6579816032,0.1122997618 H,-5.8742629217,-2.0312378882,2.2999016958 H,-7.2251749303,-0.2670574682,1.1923790781 C,-1.0191170246,2.4009386828,-1.3427712129 C,-0.7246125585,5.1885503712,-1.2574235316 C,-1.8846739225,3.2416429824,-2.0657987107 C,-0.0242309167,2.9831493261,-0.5421759179 C,0.1140705275,4.3660929616,-0.5080918698 C,-1.7304987707,4.6210854274,-2.0365587133 H,-2.6745835207,2.7989903627,-2.6675485431 H,0.6205406404,2.3632200824,0.0659281774 H,0.8839777067,4.8044686834,0.11884054 H,-2.3974336144,5.2515273475,-2.6156814994 H,-0.6031826309,6.2665954828,-1.2243222506 285 TS-Z,E[1,1]benzene (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,E- diimine 1 complex in benzene) cydiimph2_ZE_b2cat2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.125183 Zero-point correction= 0.571907 (Hartree/Particle) Thermal correction to Energy= 0.602875 Thermal correction to Enthalpy= 0.603819 Thermal correction to Gibbs Free Energy= 0.509330 Sum of electronic and ZPE= -1696.553276 Sum of electronic and thermal Energies= -1696.522308 Sum of electronic and thermal Enthalpies= -1696.521364 Sum of electronic and thermal Free Energies= -1696.615854 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.310 127.791 198.870 H,-1.3985721388,-4.0816341597,0.4281810754 C,-0.9753757766,-3.4649108022,1.2281612946 C,-1.1678249521,-2.8366161568,3.6892429815 C,-0.5439571969,-1.1104193818,2.0224594611 C,-1.294790699,-1.3496601014,3.3272736699 C,-1.1647242787,-1.9857000415,0.9096346041 C,-1.669911367,-3.7533178856,2.5660589718 H,-0.1129910622,-3.0614186611,3.8914901194 H,0.499207944,-1.4052675129,2.1667469217 H,-2.3533760333,-1.0818269118,3.2215832725 H,-2.2347187681,-1.7676966958,0.8938849287 H,-2.752687274,-3.612050499,2.4431508002 H,0.094777018,-3.6878933471,1.2855173121 H,-1.7184536051,-3.041040392,4.6121467506 H,-0.8730680827,-0.7190790913,4.1155864477 H,-1.5179808918,-4.8005938114,2.8429561758 N,-0.5023665798,0.2799075499,1.5290466795 N,-0.6030728309,-1.5313736621,-0.3763231642 C,-1.6709328859,0.8481516057,1.2837478854 H,-2.5651161746,0.2423663666,1.4262359401 C,-1.3642044791,-0.990058594,-1.2980939936 H,-0.8128984294,-0.4930562383,-2.094119986 B,0.7376307434,0.5294299151,0.669287442 B,0.8645714517,-1.1743928689,-0.3287961289 O,1.729642797,-2.1136385964,0.3591538018 O,1.4894050295,-0.820977504,-1.5781889353 O,2.0283497294,0.6614378456,1.3052302505 286 O,0.6223014105,1.5400234055,-0.3471008268 C,2.751246682,-1.327599727,-1.5035806056 C,5.1557739905,-2.5403657109,-0.9258568677 C,3.7973425974,-1.1406670534,-2.3829116717 C,2.8951419291,-2.0991480774,-0.3425475523 C,4.0888537296,-2.7175090362,-0.0312344737 C,5.0138353718,-1.7686862638,-2.074136449 H,3.6755304671,-0.5248814711,-3.2669012549 H,4.1897558641,-3.3094310735,0.8717080293 H,5.8588905881,-1.6418273281,-2.7428532513 H,6.1094084326,-3.0115628125,-0.7109340506 C,1.8726977419,2.0589184321,-0.4726008781 C,4.5197435098,2.811933435,-0.3479464603 C,2.3281736384,2.9780698672,-1.3958412052 C,2.7169405186,1.5269341284,0.5134362945 C,4.0488657253,1.8815612001,0.5907005625 C,3.6789235123,3.3498844395,-1.3172942669 H,1.6623940385,3.3838358887,-2.1494381765 H,4.6958130204,1.4485920593,1.3453186961 H,4.073088811,4.0663523229,-2.0307322119 H,5.5621771361,3.111843351,-0.317013498 C,-1.8978305824,2.2316878252,0.9250974395 C,-2.4825391563,4.8793284687,0.223550683 C,-0.9457273936,3.2477280461,1.1239208883 C,-3.1586562152,2.5741699772,0.4045929782 C,-3.4443684375,3.8850669024,0.0481873216 C,-1.2401988996,4.5568986673,0.7709786204 H,0.009866658,3.0095846625,1.5789518269 H,-3.9060741357,1.7956891896,0.2727552724 H,-4.41794993,4.1337724445,-0.3621365604 H,-0.4981808284,5.3328440187,0.9292278525 H,-2.7048561222,5.905555464,-0.0511157146 C,-2.8216126273,-0.9933063571,-1.4202654965 C,-5.5954606248,-0.8739749278,-1.827284635 C,-3.4065801211,0.1101855072,-2.0662303052 C,-3.6488940114,-2.0595748776,-1.0257136587 C,-5.0230185299,-1.9915207349,-1.2221819181 C,-4.7806274731,0.1726613011,-2.2574296274 H,-2.7707253994,0.9285677595,-2.3930246396 H,-3.2124771903,-2.95812311,-0.6005164507 H,-5.6484147523,-2.8239588018,-0.9161209358 H,-5.216220968,1.0396383029,-2.7438155994 H,-6.6687219717,-0.8279955019,-1.9801420014 287 TS-Z,Z[1,1]benzene (Reductive coupling transition state from dicoordinate 1,1-B2cat2-Z,Z- diimine 1 complex in benzene) cydiimph2_ZZ_b2cat2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1123544 Zero-point correction= 0.572514 (Hartree/Particle) Thermal correction to Energy= 0.603395 Thermal correction to Enthalpy= 0.604339 Thermal correction to Gibbs Free Energy= 0.510977 Sum of electronic and ZPE= -1696.539841 Sum of electronic and thermal Energies= -1696.508959 Sum of electronic and thermal Enthalpies= -1696.508015 Sum of electronic and thermal Free Energies= -1696.601377 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.636 127.733 196.497 H,-1.2109770647,-3.1753641051,1.6970470036 C,-0.8568364144,-2.2524079318,2.1688147651 C,-1.2236804236,-0.6127945746,4.0636669013 C,-0.5592887704,0.2454391005,1.8403240475 C,-1.4279675287,0.5324071542,3.0624978223 C,-1.0016133024,-1.0878039437,1.19175344 C,-1.6379847996,-1.9548151231,3.4522206166 H,-0.169385581,-0.6565051352,4.3653087445 H,0.4676186153,0.1414591205,2.2027115292 H,-2.4862219716,0.5736898359,2.7974438678 H,-2.0497678052,-0.9453246455,0.9161052009 H,-2.7130250819,-1.9280343542,3.2275794033 H,0.2065749566,-2.3876001483,2.391891688 H,-1.8080192446,-0.4142764034,4.966933607 H,-1.1471258276,1.4938513083,3.503508442 H,-1.4839858678,-2.7647814584,4.1712005122 N,-0.4548649602,1.2188412817,0.7154648823 N,-0.2302623825,-1.2805811421,-0.0549720169 C,-1.4669801759,1.5726999818,-0.0538442717 H,-1.1719920557,2.0026921216,-1.0077453169 C,-0.8272076062,-1.380457458,-1.2318003759 H,-0.1384526093,-1.3269908813,-2.0716670859 B,0.908540555,1.1235738934,0.0864008046 B,1.1974637456,-0.8682385985,0.0073533071 O,1.9594608761,-1.2701495687,1.1708421428 O,2.0173790669,-1.051794346,-1.1608276417 O,2.0703719241,1.5446078839,0.833950389 288 O,1.0089846419,1.639411524,-1.2520758913 C,3.2723289151,-1.2729375217,-0.6763952675 C,5.5948833753,-1.6878900469,0.7432996952 C,4.4556115167,-1.346723548,-1.3810105682 C,3.237290854,-1.3950569973,0.7195642232 C,4.3871553183,-1.6031913633,1.4534228059 C,5.6286304052,-1.5618401771,-0.641432026 H,4.4679990923,-1.2278931274,-2.458556859 H,4.3493927739,-1.6907291429,2.5335574576 H,6.5785343973,-1.6219510249,-1.1624263231 H,6.518513281,-1.8501151982,1.2894415986 C,2.3000836255,2.0616160913,-1.3622313258 C,4.9449588386,2.7855234769,-1.1038785695 C,2.9671167806,2.486894761,-2.4921856046 C,2.9345774235,2.0007684267,-0.1130757149 C,4.2609115196,2.3506044381,0.0409317406 C,4.3130752799,2.8544524706,-2.3414665729 H,2.4659087892,2.5247330637,-3.4529950094 H,4.7464235338,2.2744053467,1.007326039 H,4.8700542448,3.1909622605,-3.2098479722 H,5.9898151048,3.0660855086,-1.0197899502 C,-2.9005246568,1.6269417735,0.2812824927 C,-5.6428675163,1.9388311751,0.7777354656 C,-3.3480921963,2.331454734,1.4103866121 C,-3.8504386279,1.1324761353,-0.6234851598 C,-5.21056827,1.2735516369,-0.3662937663 C,-4.7072389558,2.4800234081,1.6582121923 H,-2.6210289959,2.7869176551,2.0750012638 H,-3.5217918517,0.6311682606,-1.5278782299 H,-5.9310335981,0.8661984165,-1.0682938909 H,-5.0362716345,3.032849582,2.5322818043 H,-6.7041450653,2.0550695498,0.97304409 C,-2.2140551399,-1.6432694981,-1.5777921066 C,-4.8438857918,-2.06815887,-2.5064418022 C,-2.584350084,-1.325744938,-2.9026749633 C,-3.1849969032,-2.2441077388,-0.7527153011 C,-4.4830763975,-2.4373439454,-1.2133696198 C,-3.8784954485,-1.5246415584,-3.3566184077 H,-1.8386698075,-0.8929883205,-3.5640022489 H,-2.9251151883,-2.6010386275,0.2371680874 H,-5.2148379314,-2.8966889439,-0.5563404808 H,-4.1374959396,-1.2558272774,-4.3757628725 H,-5.8586479469,-2.2240207034,-2.8575264721 289 TS-E,E[1,2]benzene (Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,E- diimine 1 complex in benzene) cydiimph2_EE_b2cat2_1-2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1302657 Zero-point correction= 0.572234 (Hartree/Particle) Thermal correction to Energy= 0.602816 Thermal correction to Enthalpy= 0.603760 Thermal correction to Gibbs Free Energy= 0.511665 Sum of electronic and ZPE= -1696.558032 Sum of electronic and thermal Energies= -1696.527450 Sum of electronic and thermal Enthalpies= -1696.526506 Sum of electronic and thermal Free Energies= -1696.618600 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.273 127.884 193.830 H,1.9675566224,2.5204032284,3.2933576883 C,2.2083089844,2.6343512658,2.231802932 C,2.7841356585,4.3307110808,0.4091002418 C,1.3269038668,2.4070851761,-0.1234730294 C,1.5906808889,3.8726831971,-0.4451229889 C,1.000192137,2.2635797576,1.379430576 C,2.5606505021,4.0958912684,1.9100868994 H,3.6762165085,3.7775671208,0.088914784 H,2.2402819768,1.8505407996,-0.3414823081 H,0.7119510123,4.4893061271,-0.2183284242 H,0.2196577116,2.995041635,1.6181486255 H,1.7456089064,4.7451861974,2.2573227183 H,3.0475558944,1.9738710675,2.0020383138 H,2.9860816889,5.390132358,0.2252625082 H,1.8089771406,3.9882125344,-1.5108500256 H,3.4550124343,4.3896049088,2.4674177279 N,0.2488034513,1.7182334868,-0.8533266665 N,0.3799758652,0.9322927741,1.5917552848 C,-0.9719282347,2.2327661108,-0.6969630561 H,-1.0426881422,3.1495890848,-0.1172042156 C,-0.9275143633,0.9770192929,1.826779292 H,-1.3804365577,1.9574869288,1.9218500311 B,0.5031927073,0.243404992,-0.9662315123 B,1.1062448156,-0.2136405256,0.9669882436 O,2.518406553,-0.0529252235,0.9757845865 O,1.6458154156,-0.1528593268,-1.7139315196 O,0.6972721461,-1.5527935182,1.1256624381 290 O,-0.6884903579,-0.5001230618,-1.0809598467 C,2.7484506338,-0.8262714638,-1.2920976704 C,5.1139421409,-2.1256589635,-0.5566850111 C,3.4849275935,-1.5388290768,-2.2350185648 C,3.20210041,-0.7737683954,0.0370151234 C,4.3784678941,-1.4230170532,0.393590347 C,4.6623630507,-2.1859047245,-1.8720913032 H,3.1139293517,-1.5646009845,-3.2542765933 H,4.6982602622,-1.3609553021,1.4287601887 H,5.2239075739,-2.7356938665,-2.6202023853 H,6.0309098767,-2.6273467989,-0.2661343712 C,-0.7632722411,-1.8214962571,-0.7750540973 C,-1.0489228049,-4.5050232577,-0.083373681 C,-1.5799925528,-2.6550246726,-1.5313434989 C,-0.0898285993,-2.3299521579,0.3432100722 C,-0.235473716,-3.6728227111,0.6793969694 C,-1.7260095506,-3.9957657103,-1.1885620917 H,-2.0999259046,-2.2211373788,-2.379500197 H,0.296771108,-4.0393989423,1.5511180973 H,-2.3656820122,-4.6378452897,-1.7849426496 H,-1.1538055746,-5.5496940577,0.1905625445 C,-2.1564990432,1.9011262373,-1.4723228062 C,-4.506111976,1.4433565403,-2.941952444 C,-3.3952258313,2.4000052862,-1.0305191428 C,-2.1144163196,1.195537939,-2.6866217814 C,-3.2809064012,0.9709153682,-3.4081584369 C,-4.5581237802,2.166719013,-1.7501860752 H,-3.43544067,2.9676460729,-0.1032748057 H,-1.1627853176,0.8503790547,-3.0742368734 H,-3.2308518093,0.4287455243,-4.3473183284 H,-5.5051038579,2.5521855287,-1.3859256937 H,-5.4128035688,1.2618217555,-3.5099020691 C,-1.7551615774,-0.190853369,2.1350259209 C,-3.3977778994,-2.3775958766,2.7204161309 C,-3.0334211772,-0.2899882315,1.5693948761 C,-1.3184923871,-1.1888343445,3.0184973906 C,-2.1376755115,-2.2733558874,3.3064297319 C,-3.8439846015,-1.3821799801,1.8537244855 H,-3.3693747325,0.473725926,0.8734636356 H,-0.3366195663,-1.1066766255,3.4725080603 H,-1.7893204271,-3.0427012596,3.9883900727 H,-4.8216903543,-1.4611213375,1.3894055641 H,-4.0297373623,-3.2324810074,2.9387150621 291 TS-E,Z[1,2]benzene (Reductive coupling transition state from dicoordinate 1,2-B2cat2-E,Z- diimine 1 complex in benzene) cydiimph2_EZ_b2cat2_1-2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1222623 Zero-point correction= 0.572688 (Hartree/Particle) Thermal correction to Energy= 0.603067 Thermal correction to Enthalpy= 0.604011 Thermal correction to Gibbs Free Energy= 0.512897 Sum of electronic and ZPE= -1696.549575 Sum of electronic and thermal Energies= -1696.519195 Sum of electronic and thermal Enthalpies= -1696.518251 Sum of electronic and thermal Free Energies= -1696.609365 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.430 127.575 191.765 H,1.4579277108,-1.6016226126,3.4842285387 C,1.4175724619,-2.1223347188,2.5223054833 C,2.6511366699,-3.7354602427,0.9893327139 C,1.4648838764,-1.8082220419,0.0076460688 C,2.710013425,-2.6818179414,-0.1277779316 C,1.4870157225,-1.103809345,1.3882300174 C,2.6027554435,-3.0867889275,2.3779503866 H,1.762521741,-4.3639224203,0.8488449492 H,0.6118684681,-2.4885376189,-0.0170639548 H,3.6258175504,-2.0965439137,-0.0150250282 H,2.4542922628,-0.5925616493,1.4640147643 H,3.5397220316,-2.5399810159,2.5491991854 H,0.4719861044,-2.6660000204,2.4736507683 H,3.5224041659,-4.3929785766,0.9144824659 H,2.7303624176,-3.1620806195,-1.1108431745 H,2.5415943183,-3.8586339785,3.1508144102 N,1.1119489229,-0.7433085413,-0.9666310446 N,0.4539999528,-0.0382048834,1.3851207234 C,1.8451207442,0.3507365711,-1.1156344287 H,1.3209124307,1.17432482,-1.5918291319 C,0.9658445011,1.1770580787,1.2609526426 H,2.0413784893,1.2661288645,1.3598809413 B,-0.3896604739,-0.6024286165,-1.0385741871 B,-0.9019900898,-0.454900739,0.8654040431 O,-1.2611442991,-1.7677630354,1.3096035805 O,-1.0665057841,-1.7794960577,-1.4981267607 O,-1.9920650579,0.4556800203,0.90128751 292 O,-0.7367923715,0.6377039525,-1.6502141931 C,-2.0881650417,-2.4033842895,-0.8564887135 C,-4.1313776821,-3.8438527251,0.3968006493 C,-3.0204463372,-3.1083239483,-1.6131005245 C,-2.1871236288,-2.4169994665,0.5458538702 C,-3.2072626485,-3.1346982078,1.1601005729 C,-4.0384619354,-3.8267626803,-0.99190655 H,-2.9209331776,-3.082608664,-2.6933574752 H,-3.254192669,-3.1237309262,2.244336719 H,-4.756590092,-4.3711738114,-1.5964124563 H,-4.9221135517,-4.4011141115,0.8881427823 C,-1.8901279067,1.2967385541,-1.3689321463 C,-4.194964971,2.7768884447,-0.8257545072 C,-2.4495294525,2.1162475374,-2.3454039571 C,-2.4897677885,1.2176276482,-0.1016557205 C,-3.6407026301,1.9598801891,0.1542942784 C,-3.5961461438,2.85828307,-2.079820545 H,-1.957905142,2.1567601564,-3.3121562582 H,-4.081200509,1.8792662342,1.142942426 H,-4.0190349912,3.4919013061,-2.8524722577 H,-5.0916450577,3.3470984915,-0.6060318889 C,3.3202572811,0.4486715611,-1.0705138592 C,6.1055337976,0.7669542584,-1.2251625519 C,3.9499167418,1.5518227173,-0.4768950171 C,4.1076142905,-0.4636700897,-1.7879070407 C,5.4882087549,-0.3105386572,-1.8556119546 C,5.3306441209,1.7032011796,-0.5448049111 H,3.3536710568,2.3001398393,0.0375371073 H,3.6244775029,-1.2817151451,-2.3125996106 H,6.0801392646,-1.0279618992,-2.4148479887 H,5.8006060484,2.5574363244,-0.0683380877 H,7.1827766065,0.8861623641,-1.2786828601 C,0.1730991126,2.4155962525,1.2610764757 C,-1.2758934929,4.8074637126,1.2726470356 C,-0.8299259905,2.6309703773,2.2156589886 C,0.4543827318,3.4206569032,0.3278417636 C,-0.2717380058,4.6066696325,0.3293788236 C,-1.5474577317,3.8207012445,2.2187293949 H,-1.0422329511,1.8578789194,2.9465024098 H,1.2240590105,3.2548882775,-0.4216114616 H,-0.0609030825,5.3682864016,-0.4141905389 H,-2.3267208528,3.9756469761,2.9582444387 H,-1.8480515916,5.7296321077,1.269365269 293 TS-Z,E[1,2]benzene (Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,E- diimine 1 complex in benzene) cydiimph2_ZE_b2cat2_1-2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1318243 Zero-point correction= 0.572967 (Hartree/Particle) Thermal correction to Energy= 0.603430 Thermal correction to Enthalpy= 0.604375 Thermal correction to Gibbs Free Energy= 0.512733 Sum of electronic and ZPE= -1696.558857 Sum of electronic and thermal Energies= -1696.528394 Sum of electronic and thermal Enthalpies= -1696.527450 Sum of electronic and thermal Free Energies= -1696.619091 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.658 127.452 192.875 H,0.8380990415,-3.995844901,1.2389279153 C,0.459186757,-3.6761530979,0.2623884669 C,0.6424748352,-4.0532795337,-2.257127898 C,0.2755125644,-1.774106133,-1.3738300155 C,0.9505957174,-2.5649472323,-2.4872652555 C,0.8516490743,-2.2299894275,-0.0124457276 C,1.0604892886,-4.5350985682,-0.8605025479 H,-0.4365588706,-4.2095236805,-2.38130696 H,-0.7913653092,-2.0012454389,-1.3991687755 H,2.0356507119,-2.4007772265,-2.4811273219 H,1.9385110577,-2.1921261509,-0.105513703 H,2.1560593285,-4.5032627594,-0.7824616044 H,-0.6310590518,-3.7635130299,0.2860275819 H,1.1396577987,-4.6570378841,-3.0220909568 H,0.5714886576,-2.2371096896,-3.4596817925 H,0.7657847121,-5.579924132,-0.725706893 N,0.3724027893,-0.3020401366,-1.4223224972 N,0.474130727,-1.2079876447,0.9844526188 C,1.6015660026,0.1991863415,-1.3695440629 H,2.4180142666,-0.5174669534,-1.3130976655 C,1.4187636294,-0.4156830962,1.4687267379 H,1.0406425666,0.4838176255,1.947139216 B,-0.8474581714,0.3383736981,-0.825247754 B,-0.9300263061,-0.7106052425,0.933014436 O,-1.8967402813,-1.733493052,0.6943328249 O,-2.0725097215,0.0122813,-1.4829516645 O,-1.2401538741,0.2571367266,1.9332485088 294 O,-0.6630401596,1.6662960833,-0.3611219107 C,-3.1933203119,-0.4183693884,-0.8430128581 C,-5.5252814684,-1.3878502562,0.3509764927 C,-4.4399185999,-0.018158216,-1.3123465469 C,-3.1155248487,-1.3091424715,0.241021399 C,-4.2794892565,-1.785484923,0.8316716523 C,-5.6037723008,-0.5017418297,-0.7191475296 H,-4.4722849029,0.6729408601,-2.1482132953 H,-4.183855844,-2.4712763774,1.6672788358 H,-6.5699074536,-0.1815568399,-1.0952450612 H,-6.4285330834,-1.7664072724,0.8178372635 C,-1.5967709469,2.1524407413,0.5084902088 C,-3.4244809888,3.1537535697,2.3525274508 C,-2.2169490553,3.3725326678,0.2764601242 C,-1.8898451805,1.4234040379,1.6718652658 C,-2.8054322094,1.9274296004,2.5877898797 C,-3.1298256747,3.8776965415,1.2012259303 H,-1.9628743135,3.9137945672,-0.6293361276 H,-3.0174255004,1.3437946787,3.4774768939 H,-3.6102385106,4.8327786642,1.0165358119 H,-4.1384752947,3.5397247977,3.0726972252 C,1.9995567475,1.5749852933,-1.6009361233 C,2.9557447395,4.1670263012,-2.094224991 C,3.3281086618,1.9249061712,-1.2948732798 C,1.1715831272,2.5389011788,-2.204371495 C,1.6508098451,3.8201568293,-2.4422864049 C,3.7964922222,3.2106214464,-1.5261645749 H,3.9880216452,1.1733049925,-0.8695265472 H,0.1665414588,2.2719326315,-2.5068498611 H,1.0030813302,4.5530774397,-2.9130510515 H,4.8211621989,3.4649904997,-1.2738287917 H,3.3213697373,5.1711815795,-2.2835839564 C,2.8500876156,-0.6612117797,1.615697821 C,5.6183151182,-0.9282219987,2.0221536266 C,3.67147347,0.4718704443,1.7654551842 C,3.439956784,-1.9336046883,1.72893505 C,4.8107663002,-2.0593533504,1.9211176835 C,5.0401030434,0.3390908683,1.9546281042 H,3.2205842742,1.4591803443,1.7129089055 H,2.8208477845,-2.824958525,1.7110266298 H,5.2480029481,-3.048571286,2.0114923659 H,5.6566976726,1.2266980772,2.0548837754 H,6.6873021496,-1.0334781555,2.1753027558 295 TS-Z,Z[1,2]benzene (Reductive coupling transition state from dicoordinate 1,2-B2cat2-Z,Z- diimine 1 complex in benzene) cydiimph2_ZZ_b2cat2_1-2_ts_benzene M062X/6-31G(d,p) E(RM062X) = -1697.1195834 Zero-point correction= 0.573052 (Hartree/Particle) Thermal correction to Energy= 0.603520 Thermal correction to Enthalpy= 0.604465 Thermal correction to Gibbs Free Energy= 0.512783 Sum of electronic and ZPE= -1696.546531 Sum of electronic and thermal Energies= -1696.516063 Sum of electronic and thermal Enthalpies= -1696.515119 Sum of electronic and thermal Free Energies= -1696.606800 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 378.715 127.525 192.960 H,-1.1908543106,-1.6593221126,-3.171204392 C,-0.8111565808,-2.126069503,-2.2557283942 C,-1.1429527619,-4.0187196919,-0.5997753247 C,-0.4516297409,-1.7971371563,0.2323173738 C,-1.3118198546,-3.0176458757,0.5528201638 C,-0.9492552511,-1.1558671797,-1.0871940491 C,-1.5824749774,-3.41148423,-1.9362867208 H,-0.0915670901,-4.3265240936,-0.666506338 H,0.5609307084,-2.1720243683,0.0786229227 H,-2.3686645508,-2.7541902574,0.6366587193 H,-2.0048774047,-0.9321118925,-0.917487668 H,-2.6572945891,-3.1883468517,-1.8903587105 H,0.2493580105,-2.3427835093,-2.4146871603 H,-1.727006072,-4.9189638941,-0.3867064852 H,-0.9944326842,-3.4632934617,1.5005119838 H,-1.4432922272,-4.1349332536,-2.7450493308 N,-0.2809546528,-0.6577873624,1.181952924 N,-0.2544740957,0.1389852498,-1.2579389296 C,-1.282204542,0.1506072807,1.5139342678 H,-0.9746244454,1.1276634585,1.8745372854 C,-0.9616848997,1.2631495274,-1.1499424098 H,-0.345549171,2.1466678308,-1.0098321214 B,1.0914848352,-0.0896002355,1.0442116467 B,1.1982033912,0.174736094,-0.983973671 O,1.9187242965,-0.9625871452,-1.4552162772 O,2.1473115688,-1.010648712,1.315712617 O,1.814159003,1.4513687004,-1.1481443355 296 O,1.202211103,1.2341674106,1.5489634586 C,3.2452998108,-1.1782225668,0.5296522512 C,5.4893197808,-1.6708583911,-1.0555251139 C,4.4792235098,-1.4224326807,1.1222483577 C,3.1364847017,-1.1751688655,-0.8699691406 C,4.2567633048,-1.4183101666,-1.6543842351 C,5.5995996193,-1.6689491667,0.331850891 H,4.5366938622,-1.4165887995,2.2057418509 H,4.1383896029,-1.4081211959,-2.7330442976 H,6.5577282063,-1.8578143106,0.8048135818 H,6.3596167994,-1.8616065516,-1.6746635077 C,2.3018889266,1.9441073737,1.1557490304 C,4.492757555,3.4469993407,0.3249484189 C,3.0925110132,2.5958315706,2.0928497196 C,2.6081312716,2.0391461742,-0.212125684 C,3.7053504094,2.7900280359,-0.6183683974 C,4.1866932419,3.3535363697,1.6791192049 H,2.8293203853,2.5004117781,3.1412578207 H,3.9235342872,2.8451265154,-1.6797386202 H,4.7991216499,3.8619188623,2.4163545876 H,5.3470653395,4.0298142043,-0.0035002993 C,-2.6773511052,-0.2503404858,1.7641565936 C,-5.3187212844,-0.9113921205,2.4488822718 C,-3.7436807212,0.5743095706,1.3808739417 C,-2.9547223602,-1.3822078063,2.5485956647 C,-4.2627580833,-1.7119659999,2.8814790438 C,-5.0531028341,0.2364200861,1.7069113159 H,-3.546954725,1.4809316466,0.8214616327 H,-2.130986648,-1.9844297313,2.9179562009 H,-4.4566993044,-2.5878925201,3.4924260959 H,-5.8654227106,0.8787222913,1.3817848625 H,-6.3403955192,-1.1703594501,2.707872088 C,-2.3554568777,1.5387101072,-1.4673504144 C,-5.0097350252,2.3487625859,-1.9825973573 C,-2.8129942471,2.8262633676,-1.1130724595 C,-3.2512101826,0.6931583671,-2.1489592667 C,-4.5620664733,1.0943929746,-2.3864856625 C,-4.1181623992,3.2223964436,-1.3572634952 H,-2.1254550259,3.5072974067,-0.6182381054 H,-2.9250295686,-0.2660185416,-2.5337260075 H,-5.234153599,0.4209470761,-2.9088801282 H,-4.4424048263,4.2151983061,-1.0618290446 H,-6.0333187715,2.6533201307,-2.1739972339 297 P-E,E[1,1]MeOH (N,N-Diborylated product 2b from reductive coupling transition state TS-E,E[1,1]MeOH and TS-Z,Z[1,1]MeOH in MeOH) cis-diph-tetrahydroquinoxaline_1-1-dieq_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2419426 Zero-point correction= 0.575765 (Hartree/Particle) Thermal correction to Energy= 0.606691 Thermal correction to Enthalpy= 0.607635 Thermal correction to Gibbs Free Energy= 0.511105 Sum of electronic and ZPE= -1696.666178 Sum of electronic and thermal Energies= -1696.635252 Sum of electronic and thermal Enthalpies= -1696.634308 Sum of electronic and thermal Free Energies= -1696.730838 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.704 126.238 203.165 C,1.7938723875,-0.4175576646,-0.703202217 C,3.3293377535,-1.8500711783,-2.0867675304 C,0.9018312123,-2.4773835095,-1.8581902212 C,2.3295291213,-2.9992460853,-2.0155627109 C,0.762646908,-1.5576692576,-0.6427906861 C,3.2109479874,-0.9703315051,-0.8448360912 H,3.1336854087,-1.2484039147,-2.9841938795 H,0.6062041375,-1.9215662271,-2.7580362827 H,2.5778424382,-3.6406696072,-1.159675807 H,1.0014995335,-2.1389371245,0.2662824927 H,3.4632747805,-1.5608499828,0.0443655332 H,1.5789584385,0.1743431087,-1.6055373377 H,4.3515290317,-2.2320876429,-2.1722218601 H,0.2159376643,-3.3230558416,-1.7616527726 H,2.3905057234,-3.6246361833,-2.9118453574 H,3.9175926996,-0.1373138801,-0.894234602 N,-0.6147984047,-1.0269868151,-0.5029848855 N,1.6341844393,0.4559517589,0.4622268883 C,0.2858428326,1.0304777953,0.576694129 C,-0.7600058788,-0.1095242198,0.6346540635 H,-0.53380105,-0.6497994363,1.5687108537 H,0.2219013389,1.509565418,1.5561452595 C,-2.1409064747,0.507246348,0.7806771626 C,-4.6202680678,1.7653077941,1.1716192806 C,-2.5727401821,0.8512061683,2.0631973321 C,-2.9678963082,0.8041681207,-0.3079359313 C,-4.2003996309,1.4215466504,-0.1124253224 298 C,-3.8007477839,1.47964447,2.2604995625 H,-1.9408057204,0.6180329354,2.9171694794 H,-2.6582919171,0.5465948007,-1.3174928581 H,-4.8335034302,1.6363710598,-0.9679619095 H,-4.1189617143,1.7364860117,3.2663245917 H,-5.5810389986,2.2480786478,1.3213742226 C,0.0621641964,2.1299347668,-0.4543125842 C,-0.2159454115,4.2719871586,-2.2559760269 C,0.2821089696,3.4493680208,-0.0438875943 C,-0.3018369172,1.9001077592,-1.7878030879 C,-0.4401242574,2.963388116,-2.678229534 C,0.146144013,4.5131408602,-0.9327411476 H,0.565265071,3.6421190287,0.9883257674 H,-0.4914032218,0.8876561886,-2.1288104766 H,-0.7262391587,2.7655453537,-3.7069557157 H,0.3193915178,5.5287516241,-0.5897896125 H,-0.3254613541,5.0975262708,-2.9526242581 H,-5.2348747295,-3.341924901,0.7197243923 C,-4.873093155,-3.4531115879,-0.2963962929 C,-3.8882696973,-3.7289928835,-2.9669974184 C,-3.6702296826,-2.9067823188,-0.6946312465 C,-5.5917346699,-4.1555911309,-1.272865234 C,-5.111228109,-4.2902027281,-2.5757812445 C,-3.1922736298,-3.0381352888,-1.9963514842 H,-6.5432095643,-4.6040408112,-1.0065558077 H,-5.6959695498,-4.8404387094,-3.3056196649 H,-3.5052465076,-3.8249231248,-3.9768743415 O,-1.9887076532,-2.3838279515,-2.1036069261 O,-2.7667504435,-2.1842785557,0.0452821356 B,-1.7326301625,-1.8462419499,-0.8360507376 H,6.4584711391,0.3376000732,2.713463636 C,5.7032574088,0.9816485904,3.1502494888 C,3.6900445315,2.6675563579,4.2759887984 C,4.434742633,1.0647423446,2.6153343905 C,5.9582229664,1.7703301535,4.2813110676 C,4.9758147009,2.5928742075,4.8306106735 C,3.4527731141,1.8867460836,3.1639423102 H,6.9428071964,1.7367768962,4.7361241345 H,5.2075208663,3.1900844544,5.7064039508 H,2.9175118813,3.3036806227,4.6936963244 O,2.2993574187,1.768679838,2.4296939757 O,3.9234939165,0.4072303775,1.522738602 B,2.5931780492,0.8420857922,1.4075781694 299 P-E,Z[1,1]MeOH (N,N-Diborylated product 2a from reductive coupling transition state TS-E,Z[1,1]MeOH in MeOH) trans-dieq-diph-tetrahydroquinoxaline_1-1-dieq_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2425235 Zero-point correction= 0.575788 (Hartree/Particle) Thermal correction to Energy= 0.606884 Thermal correction to Enthalpy= 0.607828 Thermal correction to Gibbs Free Energy= 0.510274 Sum of electronic and ZPE= -1696.666735 Sum of electronic and thermal Energies= -1696.635639 Sum of electronic and thermal Enthalpies= -1696.634695 Sum of electronic and thermal Free Energies= -1696.732249 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.826 126.470 205.319 C,0.5614074099,-1.3933375091,1.4997579273 C,0.7542964813,-3.013146387,3.410912091 C,-1.4685194248,-1.9472485432,2.8519597283 C,-0.5854663452,-2.5206386626,3.9658711643 C,-0.7017806797,-0.8287495593,2.1501375617 C,1.4762191078,-1.9255618303,2.6086094016 H,0.5751784324,-3.8759775961,2.7556410302 H,-1.7221948719,-2.7414609615,2.1441285434 H,-0.4034770022,-1.7430819813,4.7192350174 H,-0.3836539064,-0.1336955848,2.941580673 H,1.7465849681,-1.0862043071,3.2637800658 H,0.2413798342,-2.2428388557,0.8747088135 H,1.3967723833,-3.3620734101,4.2257325689 H,-2.4053374446,-1.5504623574,3.2575856854 H,-1.1091784001,-3.3388363514,4.4703931779 H,2.4028685492,-2.3207136097,2.1848288844 N,-1.4345483646,-0.0116060413,1.1814333335 N,1.2355623417,-0.4085985247,0.6271174722 C,0.6642418949,0.903330039,0.2334288139 C,-0.6632438403,1.2169612225,0.9588862544 H,-0.3956903445,1.5726943203,1.962077296 H,0.4594229856,0.8616822679,-0.8430106599 C,-1.4795647513,2.3431437564,0.3428721854 C,-3.1171714298,4.4077394158,-0.6252915802 C,-2.4333639495,2.9490605294,1.1677546334 C,-1.3570167819,2.7864158333,-0.9748720261 C,-2.1687062762,3.8143513822,-1.4535291146 300 C,-3.2495725314,3.9696717754,0.6915121629 H,-2.5341296071,2.6096237621,2.1961703579 H,-0.6453452219,2.3274046788,-1.6525088278 H,-2.0599441988,4.1464962542,-2.481544232 H,-3.9840482189,4.4258382381,1.3482602314 H,-3.7483952389,5.206793231,-1.0019095694 C,1.6592979941,2.02544675,0.4910827527 C,3.4500687171,4.1165008373,1.0140088445 C,2.193585517,2.1996796737,1.7714423704 C,2.0415381641,2.9010860557,-0.5256465915 C,2.9314065577,3.9427967788,-0.2666269697 C,3.0809449132,3.2390669364,2.0337212687 H,1.9176353262,1.5062728237,2.5634361671 H,1.6511327986,2.7579105554,-1.5300151199 H,3.2229585687,4.6143538938,-1.0685480016 H,3.4880776784,3.3631291055,3.0327146193 H,4.1441440028,4.9264535987,1.2165409274 H,-4.7826579389,-3.7962542255,-0.3912612934 C,-4.7577940936,-2.8769108833,-0.9658667004 C,-4.6691322734,-0.4414313042,-2.4582949638 C,-3.9079743293,-1.8433289442,-0.631075439 C,-5.5815050046,-2.6721198972,-2.0819987166 C,-5.5383641997,-1.4837781311,-2.8102507956 C,-3.8641361623,-0.6568204899,-1.3591722962 H,-6.2665187136,-3.4580885167,-2.3826558597 H,-6.1906112494,-1.359315109,-3.6684543097 H,-4.6254134191,0.4883858603,-3.0147645506 O,-2.9322803812,0.1850761668,-0.8038713065 O,-3.0042719163,-1.7763989247,0.4013270377 B,-2.4033524558,-0.5106725113,0.2943695242 H,4.4529555446,-4.2491386326,-1.0780512917 C,4.5035419502,-3.288619299,-1.5787393578 C,4.6122469651,-0.7445888402,-2.8755880302 C,3.7055189874,-2.2334716389,-1.1885152773 C,5.3757254715,-3.0502358226,-2.6501026166 C,5.4286832931,-1.8089051366,-3.2830056307 C,3.7585754763,-0.9923855632,-1.8208694223 H,6.0221620911,-3.8519638331,-2.9916511751 H,6.1162179458,-1.6595484709,-4.1090302905 H,4.6441437808,0.2255330089,-3.3590075192 O,2.8608400295,-0.1375729902,-1.2263899595 O,2.7722592752,-2.1929149388,-0.1796048866 B,2.2549905305,-0.8889745757,-0.2082062056 301 P-Z,E[1,1]MeOH (N,N-Diborylated product 2c from reductive coupling transition state TS-Z,E[1,1]MeOH in MeOH) trans-diax-diph-tetrahydroquinoxaline_1-1-dieq_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2551567 Zero-point correction= 0.576348 (Hartree/Particle) Thermal correction to Energy= 0.607158 Thermal correction to Enthalpy= 0.608103 Thermal correction to Gibbs Free Energy= 0.512450 Sum of electronic and ZPE= -1696.678809 Sum of electronic and thermal Energies= -1696.647998 Sum of electronic and thermal Enthalpies= -1696.647054 Sum of electronic and thermal Free Energies= -1696.742706 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.998 126.239 201.317 C,0.5332653288,0.4104333842,-1.5855812913 C,0.5466186048,0.2736317247,-4.1026061842 C,-1.3636383844,-0.7159374226,-2.8129520514 C,-0.480153411,-0.8548606223,-4.0515859113 C,-0.517357922,-0.7159766004,-1.5424443887 C,1.4021413545,0.2900979656,-2.8362273353 H,0.0241367684,1.2341139969,-4.2034250841 H,-1.9267073437,0.2227893625,-2.8752318937 H,0.0404154924,-1.8212718025,-4.0259102316 H,0.0363788674,-1.6676715751,-1.5006017994 H,1.988991468,-0.6350987289,-2.7795459158 H,-0.0252510995,1.3585792934,-1.6441285358 H,1.1941580779,0.167898756,-4.9787890924 H,-2.0923235097,-1.5307101902,-2.7625570881 H,-1.1038647125,-0.8495476005,-4.9510840731 H,2.1101093483,1.1228244771,-2.868705766 N,-1.3149212568,-0.6170225612,-0.3133408052 N,1.3163964158,0.4268158694,-0.3390760099 C,0.4909881103,0.5253934777,0.8706589288 C,-0.4925105685,-0.6583916935,0.9003705232 H,-1.1552742491,-0.5294386134,1.7577408896 H,1.1501798789,0.4360320969,1.7372310184 C,0.1677738717,-2.0283209913,1.0820315488 C,1.2232144171,-4.6074916808,1.4797835035 C,1.4581525022,-2.2021251788,1.5892912598 C,-0.5865948375,-3.1695582731,0.7841487588 C,-0.0679016741,-4.4455712427,0.9792578389 302 C,1.9804870694,-3.481369719,1.7852585212 H,2.0788308423,-1.3488811126,1.8416661559 H,-1.5923935426,-3.0524564262,0.3896111318 H,-0.6732525761,-5.3146399098,0.7393071755 H,2.9877980247,-3.5910785547,2.1757760455 H,1.6329232219,-5.6016196631,1.6296656823 C,-0.1891312457,1.8942458335,0.9924139141 C,-1.3080256943,4.4621272524,1.2985825665 C,0.4033730518,3.0145539063,0.3993938873 C,-1.3481045701,2.0868466143,1.7524158028 C,-1.9030699196,3.3573396583,1.9009002097 C,-0.1481355457,4.2844511588,0.5482055538 H,1.305823755,2.8908264926,-0.1924567674 H,-1.836213838,1.2522680929,2.2438938685 H,-2.8056246036,3.4786278786,2.4924695043 H,0.3313014275,5.1358985032,0.0744802942 H,-1.7420627609,5.450527832,1.4133992206 H,-6.2536991178,0.1074682999,-2.1672144651 C,-6.1146844617,0.0169091551,-1.0955931254 C,-5.7138082059,-0.2243981414,1.7229897369 C,-4.8637723168,-0.1760935648,-0.547987481 C,-7.1873177816,0.0897210601,-0.1952314401 C,-6.9916863161,-0.0280323013,1.1800133325 C,-4.6680070834,-0.2945512924,0.8263954105 H,-8.1900733127,0.2410475072,-0.5811620609 H,-7.8444705653,0.0328642283,1.8481541961 H,-5.548378672,-0.3177307633,2.7906470285 O,-3.3327352556,-0.4809381984,1.080513954 O,-3.6547752447,-0.2805579547,-1.193257763 B,-2.7006535792,-0.4634052886,-0.1798817279 H,6.3338491735,0.182863751,-2.112834163 C,6.1701674826,0.3319718421,-1.0512863453 C,5.7032750454,0.7223461541,1.7405458005 C,4.8976019062,0.4093167083,-0.5254043377 C,7.2307632976,0.4550469623,-0.1423716477 C,7.0029168059,0.645464919,1.2198019022 C,4.6696385529,0.600115908,0.8355136296 H,8.2497871697,0.3999854944,-0.5109972248 H,7.847320879,0.7365348458,1.8951021006 H,5.5129185605,0.8704575138,2.7977780649 O,3.3173412427,0.6401306901,1.0675448036 O,3.694165101,0.3195099116,-1.1832075244 B,2.7103380623,0.4591220893,-0.1925262328 303 P-E,E[1,2]MeOH (N,N-Diborylated product 2b from reductive coupling transition state TS-E,E[1,2]MeOH in MeOH) cydiimph2_EE_b2cat2_1-2_product_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2129144 Zero-point correction= 0.576205 (Hartree/Particle) Thermal correction to Energy= 0.606215 Thermal correction to Enthalpy= 0.607159 Thermal correction to Gibbs Free Energy= 0.517199 Sum of electronic and ZPE= -1696.636710 Sum of electronic and thermal Energies= -1696.606699 Sum of electronic and thermal Enthalpies= -1696.605755 Sum of electronic and thermal Free Energies= -1696.695716 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.406 126.237 189.338 C,0.1346109869,2.7590343558,-0.4210047663 C,0.6231050158,5.1650624647,-0.1757456623 C,0.9404191518,3.5751341253,1.8131120873 C,0.6326253542,5.0118088532,1.3538792573 C,-0.0644836377,2.6662198335,1.1151999201 C,-0.2876585374,4.1473310003,-0.8857065166 H,1.6458657251,5.0288016369,-0.5513362318 H,1.9667754323,3.3032514521,1.5486652682 H,-0.3505543908,5.3000592823,1.7484639466 H,-1.04439811,3.1045677332,1.3496592182 H,-1.34014694,4.337912921,-0.6365825413 H,1.2043668256,2.6711291011,-0.6256130004 H,0.3237586317,6.1845248993,-0.4395288937 H,0.8383766769,3.4932690416,2.9005268399 H,1.3619174812,5.7049732827,1.7853908239 H,-0.1811639413,4.2364694237,-1.9718345922 N,-0.5138339512,1.5811289459,-1.0333077902 N,-0.1822519055,1.2486709192,1.5089177807 C,-1.557968663,0.8243405168,1.1492044384 H,-2.2225201075,1.4668419507,1.7397976974 C,-1.7946335468,1.3094814184,-0.3665488193 H,-2.2550387244,2.2954926554,-0.2415242296 B,0.9269006497,0.38093584,1.3131545979 B,0.3768209343,0.4999637108,-1.2985511529 O,1.670450693,0.7478367568,-1.7460083962 O,0.8497179217,-0.9938688379,1.5021645748 C,3.051618301,0.2850273667,0.1632042543 304 C,4.881207965,-1.0006631856,-1.4840527533 C,2.801186396,0.1761438972,-1.21286183 C,4.209558865,-0.2473672488,0.7099286729 C,5.1269126134,-0.8945102172,-0.1173190831 C,3.7183312849,-0.4637440654,-2.0351270367 H,4.3742655377,-0.1511062909,1.7784986911 H,6.0314692339,-1.3144615667,0.3097213933 H,3.5039037398,-0.53929859,-3.0964050312 H,5.5939793542,-1.5039742196,-2.1289968193 O,2.1363840036,0.9602990982,0.9358949978 C,1.1341455436,-1.9719120288,0.5903223225 C,1.6234213777,-4.025446142,-1.2347089876 C,0.674836826,-1.87311399,-0.7319645713 C,1.8378786694,-3.101633925,0.9893269207 C,2.0817038725,-4.126546894,0.0764182072 C,0.9136709342,-2.8954477212,-1.6385443052 H,2.1865075578,-3.1597276156,2.0155220391 H,2.6328630972,-5.0049920524,0.3957524493 H,0.5373319762,-2.7898801627,-2.6512680304 H,1.8121275416,-4.823759543,-1.9445836766 O,-0.0839234101,-0.7839217437,-1.079253702 C,-1.8925066001,-0.5858249784,1.6264925526 C,-2.4536279268,-3.0865268561,2.7960140242 C,-1.9817447145,-0.7336461323,3.0178653896 C,-2.1154656533,-1.7118907012,0.8303911701 C,-2.3917292245,-2.9496784489,1.4130887895 C,-2.2496526519,-1.9665661481,3.6013004964 H,-1.823157482,0.1365242352,3.6508427005 H,-2.0686162862,-1.6399744867,-0.2477058373 H,-2.5549756725,-3.8118281787,0.772926674 H,-2.3037339203,-2.0522921517,4.6824853425 H,-2.6646493273,-4.0531167161,3.2433815602 C,-2.8185564396,0.5455980588,-1.1812131193 C,-4.8369432634,-0.7795997231,-2.6189039019 C,-2.5949568842,0.1196300564,-2.490535334 C,-4.0808060274,0.3281021498,-0.6126397479 C,-5.0786831336,-0.3324541364,-1.3195230342 C,-3.5959670222,-0.5440440601,-3.2017074723 H,-1.6398839959,0.3068151478,-2.9698668931 H,-4.2800728074,0.6747626324,0.3989720685 H,-6.0472834716,-0.4968188343,-0.8569630377 H,-3.4000257881,-0.8734618874,-4.2177866562 H,-5.613419012,-1.2980462834,-3.1728697139 305 P-E,Z[1,2]MeOH (N,N-Diborylated product 2a from reductive coupling transition state TS-E,Z[1,2]MeOH in MeOH) cydiimph2_EZ_b2cat2_1-2_product_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2192208 Zero-point correction= 0.576570 (Hartree/Particle) Thermal correction to Energy= 0.606480 Thermal correction to Enthalpy= 0.607424 Thermal correction to Gibbs Free Energy= 0.518173 Sum of electronic and ZPE= -1696.642651 Sum of electronic and thermal Energies= -1696.612741 Sum of electronic and thermal Enthalpies= -1696.611797 Sum of electronic and thermal Free Energies= -1696.701048 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.572 126.268 187.845 C,-0.0813756064,2.3484319466,0.1366000006 C,-0.2883670983,4.6666491007,0.921281779 C,0.3929170111,2.796470084,2.5494670701 C,-0.2741172288,4.1744578873,2.3788447093 C,-0.31180252,1.8554581265,1.5809073901 C,-0.8714700301,3.6390650953,-0.0673946983 H,0.7407598669,4.893566763,0.6130253285 H,1.4626351706,2.86002957,2.3297119918 H,-1.3080726937,4.1058837948,2.7415223712 H,-1.379201842,1.9758640893,1.804391752 H,-1.938861243,3.4830472677,0.1291228677 H,0.9699497997,2.6288990295,0.0525068853 H,-0.850124966,5.6043173656,0.859945196 H,0.2775028598,2.4436635769,3.5798536878 H,0.2325225316,4.9137218475,3.0075536206 H,-0.769399002,4.003183504,-1.0954384341 N,-0.2535745316,1.206549345,-0.7834360819 N,-0.0760092068,0.3945984134,1.6246065328 C,-1.28730581,-0.1817142744,1.01613451 H,-2.1186869167,0.2894153527,1.5499828361 C,-1.3795056668,0.308271876,-0.4938941133 H,-1.2501994706,-0.5649314542,-1.1403173121 B,1.2077503888,-0.0493191727,1.1672688783 B,0.9104505481,0.6969501108,-1.4067314306 O,2.0558187714,1.4945065945,-1.4653058326 O,1.5652195276,-1.2905814862,0.6729495453 C,3.3563217487,0.6879341332,0.3988710438 306 C,5.5713846291,0.4686820725,-1.2761513075 C,3.2423069424,1.0069679057,-0.9654141997 C,4.5726863986,0.2569668467,0.9107839034 C,5.6826266618,0.1496219073,0.0745749989 C,4.3506958852,0.8955548444,-1.7955216838 H,4.633039031,0.0158303669,1.9674523539 H,6.631013281,-0.1845785617,0.4820919632 H,4.2390365003,1.1533346155,-2.8439603042 H,6.432793648,0.3866582338,-1.930808194 O,2.2693407641,0.8502218329,1.2321474333 C,1.0633125484,-2.1877927365,-0.2248313071 C,0.1504264054,-4.087048709,-2.0514052858 C,0.764428202,-1.8074463235,-1.540328373 C,0.9691185794,-3.5258852738,0.1444396325 C,0.5099216887,-4.4751528259,-0.761578555 C,0.2880464165,-2.7583733448,-2.4397488523 H,1.24521767,-3.7960280454,1.1582691917 H,0.4249993185,-5.5125648533,-0.4549069674 H,0.052945284,-2.4342764815,-3.4486394939 H,-0.2196968578,-4.8178566321,-2.7628178385 O,1.0180339333,-0.5478378036,-2.0058813595 C,-1.4989637783,-1.6650645761,1.2518561358 C,-2.1051702975,-4.3394257836,1.8543087236 C,-2.2727691844,-2.4336116136,0.37720565 C,-1.0411495338,-2.2495674905,2.4373161138 C,-1.3377791215,-3.5769313727,2.73373807 C,-2.5727137544,-3.7616293613,0.6767515755 H,-2.6563749545,-2.0046758825,-0.5448529033 H,-0.4492462546,-1.657723228,3.1288149229 H,-0.9698077055,-4.0160151078,3.6564692806 H,-3.1717292937,-4.344315301,-0.0168459801 H,-2.3375664138,-5.3743636669,2.0859265107 C,-2.724294207,0.9189204867,-0.874130222 C,-5.1907381381,1.9870868704,-1.70211908 C,-2.8014126656,1.7741122234,-1.9797843324 C,-3.9064297205,0.5907649897,-0.2038384858 C,-5.1295586043,1.1226841877,-0.6140546333 C,-4.0194327856,2.3074654658,-2.3879879913 H,-1.8920894432,2.0291321617,-2.5156350727 H,-3.8951928116,-0.093498805,0.6397408874 H,-6.0345912065,0.8574218158,-0.0759848875 H,-4.0539156145,2.9752323049,-3.2436527107 H,-6.1420578329,2.4041851611,-2.0177094198 307 P-Z,E[1,2]MeOH (N,N-Diborylated product 2c from reductive coupling transition state TS-Z,E[1,2]MeOH in MeOH) cydiimph2_ZE_b2cat2_1-2_product_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2252124 Zero-point correction= 0.576487 (Hartree/Particle) Thermal correction to Energy= 0.606418 Thermal correction to Enthalpy= 0.607362 Thermal correction to Gibbs Free Energy= 0.517712 Sum of electronic and ZPE= -1696.648725 Sum of electronic and thermal Energies= -1696.618794 Sum of electronic and thermal Enthalpies= -1696.617850 Sum of electronic and thermal Free Energies= -1696.707500 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.533 126.200 188.685 C,-0.4222676963,1.8371399012,1.407870485 C,-0.4486997316,4.0998179761,2.3706318769 C,-0.4151572329,3.7725129256,-0.1796113921 C,-0.0501844363,4.685936846,1.0053545101 C,0.1998721705,2.4124182343,0.1160554081 C,0.0587089658,2.6628707022,2.5949165988 H,-1.5439703772,4.0897709523,2.4460013366 H,-1.5021387347,3.6961598796,-0.2867975605 H,1.0351650036,4.8509071392,0.9915216924 H,1.2597260775,2.6203220606,0.3134720569 H,1.1544697183,2.6501942164,2.6642287944 H,-1.5016718055,1.9780912371,1.3478974459 H,-0.0838499549,4.7545592111,3.1684892671 H,-0.0099803355,4.1799523915,-1.1122503422 H,-0.5201340334,5.6666302135,0.879741552 H,-0.3413398438,2.2625354189,3.5323374284 N,-0.186917392,0.3779703685,1.4141930023 N,0.204062063,1.3492388511,-0.9064884858 C,1.3224231238,0.4546814898,-0.5622002518 H,1.2262779204,-0.4578180562,-1.1540553865 C,1.1851677005,0.079768224,0.9726987851 H,1.8233584453,0.7793062017,1.5282028449 B,-1.0363169879,0.7202934229,-1.219454495 B,-1.3201186307,-0.4477684588,1.1903537984 O,-2.5834881358,0.0908458491,1.4607061181 O,-1.2085864128,-0.5401088514,-1.7666554494 C,-3.3839539928,0.7012893185,-0.7310576207 308 C,-5.7729780431,-0.6287131078,-0.2001098029 C,-3.5608956334,0.0338225936,0.4936498217 C,-4.3989398904,0.6945892655,-1.6780946775 C,-5.5959631444,0.031580428,-1.4130201643 C,-4.7544285346,-0.6289847049,0.7511100984 H,-4.2360794275,1.2185703326,-2.6147368482 H,-6.386293048,0.033256943,-2.1564306788 H,-4.8691378046,-1.1339524151,1.7050328564 H,-6.7028333382,-1.1468145711,0.0104412883 O,-2.2205597162,1.4051976457,-0.9658303122 C,-0.6178509555,-1.7551142498,-1.5477003933 C,0.3627471462,-4.3375288168,-1.1831795409 C,-0.7113769251,-2.371148529,-0.2918097546 C,-0.0124619549,-2.4257121526,-2.6057743383 C,0.4859897091,-3.7128284974,-2.4228922707 C,-0.238378126,-3.6678059323,-0.122400923 H,0.0483034102,-1.9231367196,-3.5659141409 H,0.9579736221,-4.2275406065,-3.2531301309 H,-0.3367197412,-4.1257972707,0.8570097808 H,0.7402188676,-5.3442630476,-1.036255918 O,-1.3483494405,-1.7608777303,0.7495404271 C,2.6621832953,1.0836098989,-0.937964277 C,5.098075258,2.2219285096,-1.7615091342 C,2.7635943341,1.754646631,-2.162787605 C,3.8016890637,0.9909828993,-0.133843393 C,5.0100651293,1.5563500805,-0.5433223876 C,3.9675924686,2.3175816086,-2.5725805887 H,1.8829753364,1.8388196602,-2.7923942857 H,3.7692629595,0.4700164197,0.8184705366 H,5.8820941199,1.4748419366,0.0984153455 H,4.0232742348,2.8342475941,-3.5260788559 H,6.0382872763,2.6627852985,-2.0781025957 C,1.6685248393,-1.3114223789,1.3459703145 C,2.6426294285,-3.8251091938,2.1402268781 C,1.2621787065,-1.8860611956,2.5559671333 C,2.575646076,-2.011465463,0.5450139067 C,3.0622322207,-3.2564030726,0.9415969487 C,1.7390500034,-3.1336216993,2.9468550295 H,0.5640077803,-1.3519871728,3.1936470219 H,2.909296835,-1.5992210847,-0.4028265214 H,3.7627015495,-3.7846756654,0.3016955233 H,1.4061738513,-3.5650289685,3.8861925174 H,3.0156767476,-4.7978041642,2.445842093 309 P-Z,Z[1,2]MeOH (N,N-Diborylated product 2b from reductive coupling transition state TS-Z,Z[1,2]MeOH in MeOH) cydiimph2_ZZ_b2cat2_1-2_product_meoh M062X/6-31G(d,p) E(RM062X) = -1697.2147945 Zero-point correction= 0.576648 (Hartree/Particle) Thermal correction to Energy= 0.606671 Thermal correction to Enthalpy= 0.607615 Thermal correction to Gibbs Free Energy= 0.517183 Sum of electronic and ZPE= -1696.638147 Sum of electronic and thermal Energies= -1696.608124 Sum of electronic and thermal Enthalpies= -1696.607180 Sum of electronic and thermal Free Energies= -1696.697611 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.692 126.174 190.330 C,-0.0046409808,-1.9269374638,0.2984611047 C,-0.5783853573,-4.2875960995,-0.0901142964 C,-0.209272533,-2.7038900721,-2.0725051516 C,-0.9344220638,-3.9553308477,-1.5478346138 C,-0.5160344386,-1.5658986641,-1.1091194881 C,-0.8036648823,-3.1003555502,0.8620871053 H,0.4783571159,-4.5820911813,-0.0396578773 H,0.8694381618,-2.883352112,-2.12674736 H,-2.0172899779,-3.7859302346,-1.6201317211 H,-1.6093315312,-1.5064177306,-1.0701698799 H,-1.8714119431,-2.8685880206,0.9252271376 H,1.013913327,-2.3001332638,0.1844075824 H,-1.1641233047,-5.1504776303,0.2428546698 H,-0.5599185697,-2.4544680978,-3.0802449823 H,-0.7050417471,-4.813348947,-2.1878511954 H,-0.4538946311,-3.346268293,1.8707706538 N,0.1095129889,-0.6722946236,1.0691434315 N,-0.0601508207,-0.1955049355,-1.4282285043 C,-0.9446014835,0.7262983696,-0.7041680026 H,-0.4711714346,1.7064420953,-0.6959623844 C,-0.9905108997,0.2847330079,0.8390199993 H,-0.7367250938,1.183303055,1.4070183505 B,1.3384839775,0.0745321707,-1.2936435664 B,1.4151873162,-0.2297935543,1.3917436775 O,2.4570006928,-1.1604208438,1.3783106009 O,1.9363007177,1.2982539266,-1.0284589923 C,3.4803489342,-0.865731624,-0.7902654634 310 C,5.9767759229,-0.7496746944,0.4411562426 C,3.5785864264,-0.946274169,0.6102920502 C,4.6277276793,-0.7241647503,-1.5587060458 C,5.8778665493,-0.669275747,-0.9450923889 C,4.82726265,-0.8871774537,1.2168126427 H,4.5221887852,-0.6634479434,-2.637357768 H,6.7699981207,-0.56220022,-1.5531881609 H,4.8781517051,-0.9574377332,2.2987445736 H,6.9471848695,-0.7062473214,0.9245730511 O,2.2485639288,-0.9706269906,-1.4050139961 C,1.5711968455,2.3739957984,-0.2657995445 C,0.9372610607,4.5900842545,1.2976866952 C,1.4778542774,2.2450645876,1.1281938313 C,1.3651989991,3.6117722216,-0.8653223738 C,1.0450484213,4.7197095938,-0.08539597 C,1.1577651786,3.3556785053,1.9024417807 H,1.4532564586,3.681722076,-1.9448312226 H,0.8806571846,5.6806811168,-0.5611660428 H,1.0918926825,3.2297936532,2.9785590238 H,0.6866915141,5.4493849688,1.9107276512 O,1.7724773081,1.0635452243,1.7493872834 C,-2.274769785,0.9811195293,-1.3868855812 C,-4.7429380324,1.5563378548,-2.5875376156 C,-2.6353188775,0.3709950802,-2.5881668757 C,-3.1487845205,1.9105251861,-0.8107528859 C,-4.3745435872,2.1940246713,-1.4019942647 C,-3.8674788519,0.6516451004,-3.1806815491 H,-1.9508310587,-0.3248704158,-3.0645258674 H,-2.8657449935,2.4088001322,0.1143964516 H,-5.0433324871,2.9138106757,-0.9397286018 H,-4.1384150406,0.162239177,-4.1115195498 H,-5.7012368717,1.7731337452,-3.0493759443 C,-2.2806327778,-0.2241113691,1.4886501235 C,-4.4798113151,-1.188540507,2.964167197 C,-2.3064411747,-0.1509982822,2.8875496276 C,-3.3859156141,-0.7860682748,0.841605182 C,-4.4730838657,-1.2632921254,1.5747342532 C,-3.3868925003,-0.6275452635,3.6221722528 H,-1.4549320023,0.2844512751,3.4063350185 H,-3.4223082224,-0.8677152999,-0.2383537013 H,-5.3180756454,-1.6973618372,1.0488042615 H,-3.3762465526,-0.5576625014,4.7056594894 H,-5.3288503302,-1.5608953643,3.5291264331 311 P-E,E[1,1]DMF (N,N-Diborylated product 2b from reductive coupling transition state TS- E,E[1,1]DMF and TS-Z,Z[1,1]DMF in DMF) cis-diph-tetrahydroquinoxaline_1-1-dieq_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2425953 Zero-point correction= 0.576011 (Hartree/Particle) Thermal correction to Energy= 0.606943 Thermal correction to Enthalpy= 0.607887 Thermal correction to Gibbs Free Energy= 0.511207 Sum of electronic and ZPE= -1696.666584 Sum of electronic and thermal Energies= -1696.635653 Sum of electronic and thermal Enthalpies= -1696.634708 Sum of electronic and thermal Free Energies= -1696.731388 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.862 126.155 203.480 C,1.7973607242,-0.4003782701,-0.7156921395 C,3.3306401264,-1.8357814297,-2.0974837824 C,0.9022230748,-2.4583445053,-1.8691800114 C,2.3286649431,-2.9835132758,-2.0266090656 C,0.7657192242,-1.5401647697,-0.6526965595 C,3.2136984184,-0.9552461601,-0.8558174328 H,3.1355698808,-1.2341511543,-2.9950174545 H,0.6073405539,-1.8994731606,-2.7669592296 H,2.5757390319,-3.6250585091,-1.1705230828 H,1.0080390687,-2.120808228,0.2562013045 H,3.465078017,-1.5438772467,0.0344747051 H,1.5819746411,0.1893487742,-1.6192811199 H,4.3520534884,-2.2196363288,-2.1831669592 H,0.2118064651,-3.3006689323,-1.7765803602 H,2.3890396879,-3.6088605949,-2.9228782949 H,3.9222630714,-0.12409805,-0.9025337783 N,-0.611023181,-1.010069674,-0.5119356975 N,1.6371903448,0.4743886909,0.4480788489 C,0.2889637384,1.0485869103,0.5610118695 C,-0.7555010186,-0.0926853327,0.6249889479 H,-0.5250183555,-0.62921544,1.5603919742 H,0.2275519852,1.5341199677,1.5374074752 C,-2.1372496949,0.5215566938,0.7723418533 C,-4.6174591281,1.779122243,1.162330472 C,-2.5627771465,0.8799618497,2.0531563892 C,-2.969925449,0.8063363697,-0.3147309108 C,-4.2029253802,1.423343509,-0.1200029208 312 C,-3.7912372695,1.5073444486,2.2500203544 H,-1.9252983364,0.6581197791,2.9059899758 H,-2.6621305833,0.5453602172,-1.3238371606 H,-4.8399326156,1.6289602866,-0.9747812712 H,-4.1046383943,1.7748759564,3.2544835372 H,-5.5784122043,2.2613469605,1.3119277844 C,0.0632908106,2.1411475297,-0.4774452637 C,-0.2212422465,4.2707878908,-2.2934786073 C,0.285396423,3.4634879302,-0.0777407851 C,-0.3062685221,1.9022373262,-1.8079410706 C,-0.4477756567,2.9592624636,-2.7053579971 C,0.1464830055,4.5211081267,-0.9734835393 H,0.5721652745,3.6640547887,0.9518218547 H,-0.4972270093,0.8871594242,-2.1401506746 H,-0.7382167996,2.7542048689,-3.7313529601 H,0.3215766547,5.5388979694,-0.6383688854 H,-0.3333036533,5.0913389637,-2.9954181548 H,-5.176102108,-3.399431589,0.7721861797 C,-4.8327322573,-3.4907980802,-0.2522685629 C,-3.9007421204,-3.7176272201,-2.945693444 C,-3.6439417585,-2.9238482828,-0.666094242 C,-5.5636203605,-4.1878882111,-1.2233519802 C,-5.108769375,-4.2986658245,-2.5377665256 C,-3.1914648734,-3.0313331008,-1.980529677 H,-6.5041487866,-4.6510220563,-0.9438417832 H,-5.7020986467,-4.8454969966,-3.2631237714 H,-3.5390175617,-3.7958527388,-3.964895385 O,-2.001610378,-2.3624281259,-2.1034879317 O,-2.7352936893,-2.2049105049,0.0635259429 B,-1.7268830065,-1.8403163787,-0.8343188384 H,6.451023298,0.3295539264,2.7184239171 C,5.6896459565,0.9604692756,3.1634032843 C,3.6642044545,2.6131287107,4.3144140475 C,4.4230785302,1.0478061209,2.6232137368 C,5.9362865064,1.7264795371,4.3117560889 C,4.9477119664,2.5330575072,4.8734784419 C,3.4339071618,1.8546131345,3.1849489005 H,6.9189566278,1.6877934037,4.7701226579 H,5.1726233291,3.1128894212,5.7625305479 H,2.8879143907,3.2374225817,4.7427366301 O,2.2869541182,1.7462356197,2.4458766444 O,3.9212435347,0.4123647059,1.5175502735 B,2.5906090486,0.8433762883,1.4070226411 313 P-E,Z[1,1]DMF (N,N-Diborylated product 2a from reductive coupling transition state TS- E,Z[1,1]DMF in DMF) trans-dieq-diph-tetrahydroquinoxaline_1-1-dieq_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2417054 Zero-point correction= 0.575872 (Hartree/Particle) Thermal correction to Energy= 0.607022 Thermal correction to Enthalpy= 0.607966 Thermal correction to Gibbs Free Energy= 0.509688 Sum of electronic and ZPE= -1696.665833 Sum of electronic and thermal Energies= -1696.634683 Sum of electronic and thermal Enthalpies= -1696.633739 Sum of electronic and thermal Free Energies= -1696.732017 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.912 126.449 206.844 C,1.565783031,-1.2013841343,-0.2471728258 C,3.0195440762,-3.245317688,-0.4767251366 C,0.5529293514,-3.3661957752,-0.9927509749 C,1.7724578427,-4.1325281172,-0.4709420432 C,0.3483794051,-2.1157995081,-0.1394920903 C,2.7885728836,-1.9468265796,0.3007825093 H,3.2793308846,-2.9983419271,-1.5147346571 H,0.7146147108,-3.0925660237,-2.0386283412 H,1.5755101517,-4.4765811558,0.552855702 H,0.3010927167,-2.4637991556,0.9050889836 H,2.6061466891,-2.1709235183,1.3607449574 H,1.7278193607,-1.0049701228,-1.3190019525 H,3.8735982899,-3.7848703498,-0.0550891586 H,-0.3479984596,-3.9875867181,-0.9500604845 H,1.9379691428,-5.0249396745,-1.0828051726 H,3.6733579322,-1.3076163618,0.2474243121 N,-0.8875439558,-1.354806974,-0.3516817688 N,1.3427582131,0.0856437556,0.4362078784 C,0.0457667618,0.5176288876,0.9941246691 C,-1.1021168678,-0.5262391585,0.8386959013 H,-1.0295363275,-1.2085214377,1.6953294083 H,-0.2618145918,1.4158524514,0.4481973551 C,-2.4483510332,0.1643037614,0.9574483968 C,-4.919768354,1.4417894672,1.3144253133 C,-3.3619309561,-0.3030649694,1.9028946701 C,-2.7869207265,1.2857509622,0.1918923768 C,-4.0130006236,1.9179010499,0.3665028481 314 C,-4.5925459225,0.3284051625,2.0820354561 H,-3.1041107837,-1.1663862714,2.5109887545 H,-2.0978415587,1.6597046949,-0.5602828118 H,-4.2628102017,2.7846764449,-0.2376646858 H,-5.2888414872,-0.0473760456,2.8253483475 H,-5.8744494541,1.9397604534,1.4533435227 C,0.1572085409,0.8890621835,2.4644115579 C,0.2608460168,1.5080829177,5.1946216397 C,0.870799251,0.0758630971,3.348281349 C,-0.5041013803,2.0137324095,2.9605337692 C,-0.4532310778,2.323111981,4.3186498882 C,0.9233507421,0.3825565072,4.7055992397 H,1.3940813903,-0.796267291,2.9627894756 H,-1.0585803084,2.6515559655,2.2760739832 H,-0.9670608748,3.2042682847,4.6908579248 H,1.4834614458,-0.2556476022,5.3824316998 H,0.3044944097,1.749932681,6.2520878796 H,-1.5006051155,-2.7310273329,-5.4187005936 C,-2.3164910455,-2.1999365557,-4.9410509742 C,-4.4495705456,-0.7972039407,-3.6584400395 C,-2.2396587094,-1.7988650324,-3.622895569 C,-3.4993053691,-1.8835571654,-5.6247012533 C,-4.5402979267,-1.1988458238,-4.9988083254 C,-3.2810371175,-1.1153874432,-2.9968253052 H,-3.602731432,-2.179010801,-6.663571447 H,-5.4417308486,-0.9704719596,-5.5578773754 H,-5.2517563541,-0.2637294149,-3.1604956669 O,-2.9346168288,-0.8490289366,-1.6999815111 O,-1.2122035568,-1.9679405596,-2.7345838992 B,-1.6461091523,-1.3774179846,-1.5337515725 H,5.8928223061,1.94108548,-1.5301910195 C,5.2558589458,2.6302863724,-0.9869832968 C,3.5575544806,4.4233448103,0.4487095028 C,4.0592034406,2.2198933639,-0.4359623063 C,5.5998059538,3.9775279973,-0.807843954 C,4.7708047922,4.8527357376,-0.1071467322 C,3.2291938574,3.0956433543,0.2653487825 H,6.5320694589,4.3435336385,-1.2250901205 H,5.0681156293,5.8892729487,0.0125903833 H,2.9052441915,5.0948155254,0.995835064 O,2.1161527162,2.4226587552,0.6978375652 O,3.4880103444,0.9733460694,-0.4627236054 B,2.2839595201,1.1072523486,0.2436656435 315 P-Z,E[1,1]DMF (N,N-Diborylated product 2c from reductive coupling transition state TS- Z,E[1,1]DMF in DMF) trans-diax-diph-tetrahydroquinoxaline_1-1-dieq_dmf M062x/6-31G(d,p) E(RM062X) = -1697.2564229 Zero-point correction= 0.576818 (Hartree/Particle) Thermal correction to Energy= 0.607577 Thermal correction to Enthalpy= 0.608522 Thermal correction to Gibbs Free Energy= 0.512565 Sum of electronic and ZPE= -1696.679605 Sum of electronic and thermal Energies= -1696.648846 Sum of electronic and thermal Enthalpies= -1696.647901 Sum of electronic and thermal Free Energies= -1696.743858 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.261 126.073 201.957 C,1.3961095473,-0.2563436677,-0.7428258224 C,3.0290277451,-1.7230751051,-1.9762185028 C,0.6357536574,-2.4441087335,-1.7445898664 C,2.0878316867,-2.9145104388,-1.8146432374 C,0.4412154196,-1.4568952176,-0.5964030187 C,2.8458285699,-0.7283904043,-0.83051442 H,2.8206286708,-1.2239779714,-2.931757517 H,0.3653432414,-1.9596058858,-2.689919622 H,2.3431781264,-3.4577938114,-0.8953024024 H,0.7123177757,-1.9652889263,0.342619088 H,3.1283820298,-1.2050666717,0.1156733122 H,1.1368158844,0.2369073723,-1.6933083072 H,4.0712479478,-2.0558252719,-2.0088390486 H,-0.0416600525,-3.2928008191,-1.6122972972 H,2.2073842337,-3.6160732335,-2.646225527 H,3.502458443,0.1357294259,-0.9642090746 N,-0.9451340094,-0.9896604723,-0.4614190197 N,1.1682075959,0.7132501631,0.339933081 C,-0.2239503349,1.1660467947,0.4321024845 C,-1.1284873507,-0.0604381053,0.6579878169 H,-2.1673648168,0.2739356011,0.646877518 H,-0.3080512477,1.8166793249,1.3049528703 C,-0.9218811386,-0.7544750824,2.008379814 C,-0.7145646855,-2.0819070548,4.4834871778 C,-0.4008641211,-0.1019991236,3.1296158031 C,-1.3402075766,-2.0827652392,2.1514678249 C,-1.239150616,-2.7412788347,3.3732317714 316 C,-0.2971875618,-0.7609207344,4.3550914536 H,-0.0666132568,0.928114158,3.0698734181 H,-1.7427452802,-2.6090658515,1.2903641297 H,-1.570376473,-3.7719806655,3.4568769417 H,0.1150238907,-0.2335094423,5.2100161949 H,-0.6313356146,-2.5936390062,5.4371893635 C,-0.6308547261,2.0187653884,-0.77527366 C,-1.325440785,3.717190692,-2.9132327769 C,0.3432899107,2.7606633897,-1.4527679262 C,-1.9624303599,2.151353495,-1.1833188965 C,-2.305211032,2.9901733995,-2.2433242756 C,0.0029059944,3.6000998528,-2.5101076225 H,1.3837916039,2.6734320664,-1.1529054254 H,-2.7544998852,1.6048310723,-0.6831888988 H,-3.3456481268,3.0713831568,-2.5432528533 H,0.7796069768,4.161882694,-3.0201977245 H,-1.5934134471,4.3679528901,-3.7396522357 H,-3.3453177734,-3.2199402328,-4.6576135848 C,-3.9493956879,-2.6486864258,-3.9615099928 C,-5.5153301905,-1.1366086702,-2.1117243126 C,-3.3916122599,-2.0467688138,-2.8524905088 C,-5.330442732,-2.4815297988,-4.1379984738 C,-6.0945992208,-1.7433848204,-3.2353636294 C,-4.1561006865,-1.3091724613,-1.9489715244 H,-5.8111784555,-2.9377812153,-4.9970203022 H,-7.1611175261,-1.6342686611,-3.4023142826 H,-6.099885187,-0.5604867833,-1.4030475265 O,-3.3462017483,-0.8347838623,-0.952227944 O,-2.0816381452,-2.0487361737,-2.4482849416 B,-2.0508704897,-1.2908689419,-1.2690115459 H,5.99385661,1.1470891115,2.548823303 C,5.2007444325,1.7910750859,2.9122265854 C,3.0909149807,3.4733705995,3.8502354033 C,3.928449831,1.7328556547,2.381903776 C,5.4095359985,2.7216513307,3.9400920691 C,4.3798288541,3.5424026122,4.3980736712 C,2.8986893246,2.5543010912,2.8392595297 H,6.3950672275,2.8013423039,4.3868004581 H,4.5762729024,4.2512447675,5.1956686855 H,2.282841864,4.107078626,4.1983973446 O,1.7562792313,2.2825654811,2.1342821681 O,3.4568922959,0.9216895832,1.3824340202 B,2.1050401072,1.2593554563,1.2293364605 317 P-E,E[1,2]DMF (N,N-Diborylated product 2b from reductive coupling transition state TS- E,E[1,2]DMF in DMF) cydiimph2_EE_b2cat2_1-2_product_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2123665 Zero-point correction= 0.576632 (Hartree/Particle) Thermal correction to Energy= 0.606583 Thermal correction to Enthalpy= 0.607527 Thermal correction to Gibbs Free Energy= 0.517737 Sum of electronic and ZPE= -1696.635735 Sum of electronic and thermal Energies= -1696.605783 Sum of electronic and thermal Enthalpies= -1696.604839 Sum of electronic and thermal Free Energies= -1696.694630 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.637 126.072 188.981 C,-1.9854072064,-0.4020072762,1.6739169886 C,-3.3071570498,-0.8009171038,3.7180908283 C,-0.7429808763,-0.8640075463,3.8054885906 C,-2.0617858881,-1.3713274432,4.416422752 C,-0.801424667,-1.1749081942,2.3147153407 C,-3.2917249457,-0.9920050021,2.1907299018 H,-3.3678612982,0.2752946591,3.9269846039 H,-0.631072824,0.2109896214,3.9745336844 H,-2.0808380625,-2.466524686,4.3421415029 H,-1.0372706905,-2.246886211,2.2616863458 H,-3.3635176268,-2.0585208938,1.9388449302 H,-1.9415549161,0.6297257538,2.03066041 H,-4.2066113123,-1.256225256,4.1446976739 H,0.1106743136,-1.3707602168,4.2681917026 H,-2.0974515933,-1.1261536176,5.4827309389 H,-4.1482769445,-0.4838141281,1.7358118436 N,-1.7583866363,-0.3565077449,0.2155144648 N,0.3999855271,-1.0098929947,1.4744449922 C,0.2320565747,-1.920498986,0.3157696731 H,0.1702455653,-2.9276236716,0.7462705531 C,-1.2487320809,-1.6512003228,-0.2543446959 H,-1.8551206098,-2.3949018157,0.2740941034 B,0.9543272541,0.2899525313,1.3098990705 B,-1.1431805897,0.8464234443,-0.2403075332 O,-1.4743056339,2.0668036178,0.3361706286 O,1.9741406738,0.5622872374,0.4096116469 C,0.4243169704,2.6140446289,1.6982221895 318 C,0.250070941,5.2566894004,0.8561102248 C,-0.5661921502,2.9934363686,0.7780014716 C,1.3199005359,3.5522672354,2.1901797797 C,1.2337496311,4.8780408742,1.7661126223 C,-0.6526047527,4.3156024062,0.3622100375 H,2.0774278522,3.2305464442,2.897785835 H,1.9363824266,5.6106764972,2.1486471531 H,-1.4235370254,4.5889984809,-0.3509578875 H,0.1807635145,6.287508575,0.5247685473 O,0.4513225614,1.3069843487,2.1173194766 C,1.9664525477,1.4722615454,-0.6049984003 C,2.0049210204,3.2607496353,-2.7499181282 C,0.8554872144,1.5882968731,-1.4563674199 C,3.090475904,2.2564934591,-0.8374160312 C,3.1083220141,3.1493241853,-1.907882325 C,0.8764217157,2.4735256754,-2.5244518331 H,3.9397928036,2.1558097087,-0.1694680719 H,3.9898844526,3.7580997021,-2.079770427 H,0.0041675262,2.5331167797,-3.1676815183 H,2.0187772588,3.9543131932,-3.5838357963 O,-0.2108538703,0.7497549312,-1.2554453597 C,1.4624292873,-1.9824548492,-0.5842139411 C,3.878109859,-2.2250485257,-2.0111892238 C,2.5831908123,-2.6013146034,-0.0138935467 C,1.5681820301,-1.5061853244,-1.8929103294 C,2.7670613729,-1.6268556132,-2.5971378605 C,3.7808409217,-2.7172084394,-0.7099651669 H,2.5112208275,-2.9866205894,1.0007594567 H,0.7215979501,-1.032961401,-2.3719657973 H,2.826678304,-1.2448490737,-3.6121177596 H,4.6351490934,-3.1954221088,-0.2402908589 H,4.8088953166,-2.3138262989,-2.5630902903 C,-1.4963368158,-1.9708698148,-1.7144205954 C,-1.9851083578,-2.7216341991,-4.377886537 C,-2.1809833061,-1.1167761896,-2.5787268477 C,-1.0884894987,-3.2227947648,-2.1940292263 C,-1.323619213,-3.5939128894,-3.5128051159 C,-2.4181007448,-1.4876280175,-3.90314996 H,-2.5407211518,-0.1571557007,-2.2234000324 H,-0.5740387703,-3.9106100274,-1.5267410301 H,-0.992510069,-4.5659123479,-3.8657007492 H,-2.9474909883,-0.8059164046,-4.5620589946 H,-2.1681743979,-3.0073775092,-5.4090006645 319 P-E,Z[1,2]DMF (N,N-Diborylated product 2a from reductive coupling transition state TS- E,Z[1,2]DMF in DMF) cydiimph2_EZ_b2cat2_1-2_product_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2198291 Zero-point correction= 0.576900 (Hartree/Particle) Thermal correction to Energy= 0.606741 Thermal correction to Enthalpy= 0.607685 Thermal correction to Gibbs Free Energy= 0.518748 Sum of electronic and ZPE= -1696.642929 Sum of electronic and thermal Energies= -1696.613089 Sum of electronic and thermal Enthalpies= -1696.612144 Sum of electronic and thermal Free Energies= -1696.701081 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.735 126.128 187.182 C,-0.6019671582,-1.5190744098,-1.476452346 C,-1.5208828401,-2.5399719434,-3.5118405515 C,-0.2471487893,-0.308790056,-3.633794838 C,-1.3208638583,-1.2141316321,-4.266565585 C,-0.634738575,-0.1405989273,-2.1705372326 C,-1.7663789478,-2.3552303044,-2.0020956204 H,-0.6236474692,-3.1597751359,-3.6394951001 H,0.7434840122,-0.7630776666,-3.7247662793 H,-2.2718810232,-0.6658355782,-4.2794472794 H,-1.6800909047,0.1923674506,-2.1948217479 H,-2.7240543707,-1.8499298391,-1.8296628473 H,0.3031197832,-2.0283245171,-1.8111015229 H,-2.3526684064,-3.0919938914,-3.9610761484 H,-0.2241251613,0.6629567746,-4.1385007074 H,-1.0637450903,-1.424754927,-5.309577728 H,-1.8069105852,-3.3296131609,-1.503271675 N,-0.415388547,-1.3126535549,-0.0263432946 N,0.0595635787,0.8378645104,-1.3040260959 C,-0.9134192697,1.1244357715,-0.2370179122 H,-1.8428323444,1.3667511432,-0.7623742479 C,-1.1859036955,-0.2161771096,0.5742497522 H,-0.7941284745,-0.080866147,1.5866464363 B,1.4073023237,0.5047482319,-0.9410557652 B,0.8395786604,-1.676330217,0.5228958551 O,1.6620525307,-2.5483758774,-0.1897589869 O,2.1317393835,0.9220343259,0.1586439207 C,3.1846444106,-1.0590428648,-1.3153074216 320 C,5.3184269643,-2.6180145749,-0.4291481274 C,2.9473765702,-2.1771826717,-0.4949908079 C,4.4838333157,-0.7307715004,-1.6797924063 C,5.5521602265,-1.5102800715,-1.2396133118 C,4.0168667075,-2.9494469214,-0.0573460947 H,4.6400471792,0.1363924663,-2.3136195007 H,6.5638049961,-1.2482681231,-1.5311935888 H,3.8097168627,-3.810642915,0.569728826 H,6.1462791447,-3.2284433333,-0.083805732 O,2.1227922018,-0.3272065669,-1.7964801545 C,1.9244978941,1.0661967267,1.4969840096 C,1.6394512618,1.3693001004,4.2552633895 C,1.4935193869,-0.0150985171,2.2798851123 C,2.2741718785,2.2652810155,2.1101899301 C,2.129379266,2.4222241323,3.4842127368 C,1.3323740662,0.1530339128,3.6535803414 H,2.6414653801,3.0711942003,1.4838441136 H,2.3901241311,3.3685880894,3.9466185257 H,0.9855371466,-0.6949219942,4.2353648309 H,1.5119732588,1.4847048224,5.3264761254 O,1.31687965,-1.2598016121,1.7542511505 C,-0.6309364983,2.3641408692,0.5901711726 C,-0.3273211385,4.776069442,1.9943914884 C,-1.1336039937,2.4999312642,1.8875128771 C,0.0157850637,3.4550357718,0.0001751694 C,0.1710570186,4.6492602768,0.6984031042 C,-0.9824771684,3.697974637,2.5842770029 H,-1.6538805437,1.6750029107,2.3672196471 H,0.3975314066,3.3621903817,-1.011998459 H,0.6806158347,5.4845067937,0.2270766377 H,-1.3757514752,3.7838408216,3.5928229981 H,-0.2074033197,5.7077648087,2.5385390359 C,-2.6623608681,-0.5616492352,0.7364394932 C,-5.3556190893,-1.2470907496,1.1673517888 C,-3.0324978646,-1.8853145877,1.0022642758 C,-3.6615955449,0.4157614127,0.7099250143 C,-4.997943136,0.0746927057,0.9221342859 C,-4.364526507,-2.2273482284,1.2109608166 H,-2.2644569093,-2.6523168463,1.0333565674 H,-3.4128335528,1.4587163835,0.5358793784 H,-5.7579218138,0.8495240054,0.8932939587 H,-4.6293319691,-3.2618353537,1.407945744 H,-6.3959145824,-1.5123046162,1.3279036042 321 P-Z,E[1,2]DMF (N,N-Diborylated product 2c from reductive coupling transition state TS- Z,E[1,2]DMF in DMF) cydiimph2_ZE_b2cat2_1-2_product_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2256751 Zero-point correction= 0.576772 (Hartree/Particle) Thermal correction to Energy= 0.606697 Thermal correction to Enthalpy= 0.607641 Thermal correction to Gibbs Free Energy= 0.517932 Sum of electronic and ZPE= -1696.648903 Sum of electronic and thermal Energies= -1696.618978 Sum of electronic and thermal Enthalpies= -1696.618034 Sum of electronic and thermal Free Energies= -1696.707743 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.708 126.103 188.809 C,-0.2811765011,-1.8604341554,1.1525750673 C,-0.0381090978,-4.2335166607,1.7483046895 C,2.0144526932,-2.8513320104,1.0473119341 C,1.3672046645,-4.2467586108,1.1222764648 C,1.0217297032,-1.9512065568,0.3269670451 C,-0.989428054,-3.2087320909,1.1020642768 H,0.0515970433,-3.9890204822,2.8148379894 H,2.2288678195,-2.4678125998,2.0498244444 H,1.2987902001,-4.649733702,0.1033221813 H,0.7934806014,-2.4753615663,-0.6105540609 H,-1.2143916097,-3.4955507714,0.0663241636 H,-0.0028457308,-1.692631425,2.1929557204 H,-0.472025774,-5.2367834137,1.6900837945 H,2.9579979467,-2.8994379927,0.4927915172 H,2.0105572132,-4.9277059499,1.6885623423 H,-1.9352792408,-3.1702224455,1.6524453425 N,-1.0142242273,-0.6554001162,0.7131962017 N,1.4029662625,-0.5861172708,-0.0809558019 C,0.5156276569,-0.2313804256,-1.2012813641 H,0.6050681525,0.8407632742,-1.387001796 C,-0.9735952929,-0.5429968113,-0.7531019189 H,-1.2115217143,-1.548170975,-1.1252309283 B,1.5593993795,0.3945886514,0.943387113 B,-1.0381051833,0.4377123912,1.6230548427 O,-0.8313491482,0.1563624538,2.9762656339 O,1.4614808195,1.7663496647,0.7903518026 C,1.4789346363,0.7522373238,3.3118200845 322 C,0.742375783,2.2228557133,5.5615142747 C,0.1233828361,0.8468522621,3.6780416015 C,2.4486742491,1.394301066,4.0705171232 C,2.0828064118,2.1290899024,5.1970315603 C,-0.2348849977,1.5833447962,4.8010925224 H,3.4870151161,1.3032262265,3.767642512 H,2.8471578457,2.6251084649,5.7860160255 H,-1.2853303928,1.6386413949,5.0681868276 H,0.4517155051,2.7932112061,6.43760749 O,1.8435928893,-0.0267268009,2.2364522396 C,0.615286978,2.5795303943,0.0922554245 C,-1.0675669733,4.4155516198,-1.1588922698 C,-0.7560386831,2.5914053851,0.3892228589 C,1.1298251542,3.4715175192,-0.8437997352 C,0.2889961203,4.3837510653,-1.4762843632 C,-1.5856829708,3.5236035494,-0.2250441429 H,2.1938140781,3.4399563339,-1.055560903 H,0.6991539995,5.0737995528,-2.2059770196 H,-2.6406031169,3.5188532336,0.0307912645 H,-1.7273044527,5.1293678856,-1.641258123 O,-1.2736964453,1.7722113197,1.3444701917 C,0.949197932,-0.9373935142,-2.4840278065 C,1.8592087471,-2.1559594879,-4.8490519708 C,2.317201871,-1.0093226872,-2.7742946 C,0.0451271754,-1.4853595476,-3.3982954467 C,0.4977266033,-2.0900783913,-4.571800311 C,2.7696104999,-1.6104261224,-3.9441140754 H,3.0276852706,-0.5946546139,-2.065440739 H,-1.0243841409,-1.4420307221,-3.2154076843 H,-0.2217118438,-2.5119693215,-5.2668584597 H,3.8349632113,-1.6558016172,-4.1489395807 H,2.2100331538,-2.628150106,-5.76136908 C,-2.0335924435,0.377306877,-1.3335748293 C,-4.0694112524,1.9610255473,-2.4491531166 C,-3.2967036205,0.4442902593,-0.7342436701 C,-1.8089848938,1.1091142055,-2.5031263911 C,-2.8206079135,1.8912422155,-3.0590526883 C,-4.3034961866,1.2331402944,-1.2825067452 H,-3.4884168231,-0.1245639593,0.1707071932 H,-0.839383987,1.0852997452,-2.9919232996 H,-2.6228971221,2.4550765447,-3.9656952715 H,-5.2747318113,1.276677163,-0.7988653074 H,-4.8552245973,2.5753774018,-2.8775882411 323 P-Z,Z[1,2]DMF (N,N-Diborylated product 2b from reductive coupling transition state TS- Z,Z[1,2]DMF in DMF) cydiimph2_ZZ_b2cat2_1-2_product_dmf M062X/6-31G(d,p) E(RM062X) = -1697.2155782 Zero-point correction= 0.576799 (Hartree/Particle) Thermal correction to Energy= 0.606829 Thermal correction to Enthalpy= 0.607773 Thermal correction to Gibbs Free Energy= 0.517138 Sum of electronic and ZPE= -1696.638779 Sum of electronic and thermal Energies= -1696.608749 Sum of electronic and thermal Enthalpies= -1696.607805 Sum of electronic and thermal Free Energies= -1696.698440 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 380.791 126.125 190.757 C,0.2728592879,1.3555299084,1.1702988592 C,-0.1577823059,3.6576330865,1.9223647098 C,-2.104763582,2.133445558,1.2430703205 C,-1.5779320209,3.5757416029,1.3400266837 C,-1.0860625172,1.332478528,0.444687998 C,0.8465957373,2.7711755891,1.1656256146 H,-0.1847645273,3.338536148,2.9727666881 H,-2.2307101783,1.7027629624,2.2415735904 H,-1.5747137732,4.0133896871,0.3326233082 H,-0.9758886696,1.8659812736,-0.5062651324 H,0.9846724946,3.1476241116,0.1472798916 H,0.0800310057,1.1250744405,2.2186761841 H,0.1818232468,4.6982857138,1.9156140763 H,-3.0793024998,2.1160287642,0.7423512389 H,-2.2597479739,4.1810359611,1.9458698024 H,1.822398625,2.7857146064,1.6634695304 N,1.0760032306,0.2299800034,0.6528584523 N,-1.3864264618,-0.0680972858,0.0775228012 C,-0.5773475789,-0.3809188441,-1.1065056007 H,-0.5599970448,-1.4627742013,-1.2247971529 C,0.948674061,0.0144067236,-0.8010492408 H,1.5332690469,-0.8801524805,-1.0309969014 B,-1.3345035666,-1.0422807212,1.1254377033 B,1.3228305865,-0.8473411909,1.5405134022 O,1.2102638913,-0.6158286035,2.9111228499 O,-1.0690760185,-2.397129433,0.995615358 C,-1.0091555181,-1.3815130192,3.4693968784 324 C,0.0591038246,-2.796423757,5.6202780734 C,0.3805028217,-1.3785531582,3.6929796948 C,-1.8460367654,-2.091834659,4.3197078532 C,-1.3150202421,-2.7979379523,5.3976222087 C,0.9036736388,-2.0874327381,4.7682072733 H,-2.9136440638,-2.0767906437,4.1246337233 H,-1.9773470529,-3.3471880868,6.0584351342 H,1.9771856639,-2.065747907,4.925758536 H,0.4792430316,-3.3444795507,6.4571271201 O,-1.5443119061,-0.6408009215,2.4379646487 C,-0.2541531627,-3.1176879406,0.1700539743 C,1.4131023465,-4.6682849662,-1.436466376 C,1.1396811447,-2.9665472074,0.2543779273 C,-0.8003102509,-4.0545837259,-0.7011524346 C,0.0310046203,-4.8280129852,-1.5070955551 C,1.9644136211,-3.7427434108,-0.5544810825 H,-1.8801381014,-4.1565510323,-0.7378559429 H,-0.4043284966,-5.5522710598,-2.1872477686 H,3.0382252272,-3.608287288,-0.4723370165 H,2.0667552168,-5.2663356856,-2.0625129904 O,1.7038396883,-2.128782418,1.1691388491 C,-1.1709334833,0.1094011317,-2.4133076522 C,-2.2086510315,0.9325633994,-4.8847990534 C,-2.3739219286,0.8124314426,-2.4754024257 C,-0.5101681094,-0.2090576681,-3.6056219351 C,-1.0208087152,0.2016225079,-4.8316835152 C,-2.8853362324,1.2292149778,-3.7053721501 H,-2.9141257415,1.0331034175,-1.5593169042 H,0.4171655196,-0.7770929732,-3.5676520928 H,-0.4938863261,-0.0490670254,-5.7473017252 H,-3.8184176165,1.7836983861,-3.7378597451 H,-2.6074704793,1.2576675738,-5.8406457294 C,1.6551662699,1.1401511154,-1.5623315278 C,3.2226685196,3.1480339479,-2.7683559886 C,3.0543786874,1.1096639995,-1.4944062765 C,1.0555869589,2.1972746112,-2.2541143173 C,1.8343821183,3.1904586155,-2.849911757 C,3.8339218614,2.0983072954,-2.0848107553 H,3.5357325147,0.2941903064,-0.9587029098 H,-0.0219608524,2.2728822729,-2.3382339866 H,1.3447118436,4.0022727534,-3.3790587026 H,4.9160807189,2.0475329343,-2.0133241671 H,3.8231977432,3.9232351832,-3.2340744463 325 P-E,E[1,1]benzene (N,N-Diborylated product 2b from reductive coupling transition state TS-E,E[1,1]benzene and TS-Z,Z[1,1]benzene in benzene) cis-diph-tetrahydroquinoxaline_1-1-dieq_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2433188 Zero-point correction= 0.576784 (Hartree/Particle) Thermal correction to Energy= 0.607675 Thermal correction to Enthalpy= 0.608619 Thermal correction to Gibbs Free Energy= 0.512070 Sum of electronic and ZPE= -1696.666535 Sum of electronic and thermal Energies= -1696.635644 Sum of electronic and thermal Enthalpies= -1696.634700 Sum of electronic and thermal Free Energies= -1696.731249 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.322 125.970 203.204 C,1.800991967,-0.4061348256,-0.6839109151 C,3.3493335498,-1.8529978563,-2.0388636307 C,0.9171804891,-2.4731711593,-1.8331158347 C,2.3452776567,-2.9996390957,-1.972254706 C,0.7689236783,-1.5471688365,-0.623515747 C,3.2193467097,-0.9609727503,-0.8064776438 H,3.167023438,-1.2589776534,-2.9441186076 H,0.6289928534,-1.9215443979,-2.7372789805 H,2.5832225508,-3.6371165213,-1.1104486787 H,1.0079902184,-2.1223043225,0.2908216246 H,3.465078489,-1.5383757535,0.0929294336 H,1.5924707593,0.1781319167,-1.592941009 H,4.3711444965,-2.238257627,-2.1104438655 H,0.2244959208,-3.3143114119,-1.7457671782 H,2.4154684245,-3.6312736758,-2.8632107562 H,3.9280156586,-0.1303631418,-0.8529168871 N,-0.6079014274,-1.0204687138,-0.4917928184 N,1.6281644566,0.4746135344,0.4713987499 C,0.2773336413,1.0469774259,0.5665179626 C,-0.7588062252,-0.1005850299,0.6422281852 H,-0.5146686883,-0.6342750738,1.5765186647 H,0.2108392615,1.5477094228,1.5349489359 C,-2.1478120658,0.4927011488,0.8008233211 C,-4.6472729055,1.6991218732,1.2129000647 C,-2.5890327471,0.7995968886,2.0886921473 C,-2.9756504313,0.8025240186,-0.2818853408 C,-4.2182475407,1.3933711559,-0.0763673933 326 C,-3.8266054575,1.4025227666,2.2968023832 H,-1.9570960613,0.5554497655,2.9394682411 H,-2.6545643581,0.5802577183,-1.295714808 H,-4.8512236638,1.6189775301,-0.9287361683 H,-4.1517766715,1.6307483718,3.3070384804 H,-5.616031073,2.1623632584,1.3707655156 C,0.0579681901,2.1236229086,-0.4897239852 C,-0.1984137849,4.2256757665,-2.3389117814 C,0.2967194592,3.4485613309,-0.1115547293 C,-0.3111342903,1.867877792,-1.8163162774 C,-0.4394059071,2.9116186729,-2.7300432243 C,0.171550742,4.4921937797,-1.0236411264 H,0.5888473323,3.6598086207,0.9141982102 H,-0.5096255642,0.8488257884,-2.131702673 H,-0.7301934867,2.6935799161,-3.7531526126 H,0.359653461,5.5128166688,-0.7051931045 H,-0.2996263084,5.0361899144,-3.0538395006 H,-5.201449693,-3.4046782958,0.6808062608 C,-4.8402900432,-3.4898395637,-0.3375200889 C,-3.8585801334,-3.6901505665,-3.0133162624 C,-3.6433719543,-2.9208227437,-0.7219996061 C,-5.5529161136,-4.1756994455,-1.3285338717 C,-5.0736862982,-4.2739410575,-2.6345296824 C,-3.1666971034,-3.0150620382,-2.0285766466 H,-6.4992466604,-4.6400078834,-1.0722600093 H,-5.6541109641,-4.8125894811,-3.3760008917 H,-3.4764539489,-3.7567867684,-4.0254571097 O,-1.973806578,-2.3464044944,-2.1215887093 O,-2.7475811463,-2.2123184931,0.0320322797 B,-1.724585907,-1.8393320831,-0.8417402567 H,6.4416139677,0.4206594361,2.7364088005 C,5.6752207232,1.0500088035,3.1739975076 C,3.6338457563,2.6963396071,4.3002176107 C,4.4082923139,1.1148051898,2.6330314273 C,5.9140146,1.8355005271,4.3096453006 C,4.9174928844,2.6390758704,4.8594212261 C,3.410840475,1.9190328195,3.1828710985 H,6.8969849906,1.8151903158,4.7680416725 H,5.1369078736,3.2347018582,5.7391193333 H,2.8499280317,3.3175340082,4.7180664563 O,2.2648431311,1.786955155,2.4461753507 O,3.9128292988,0.4570746267,1.5377649472 B,2.579017762,0.8728545889,1.4217118968 327 P-E,Z[1,1]benzene (N,N-Diborylated product 2a from reductive coupling transition state TS-E,Z[1,1]benzene in benzene) trans-dieq-diph-tetrahydroquinoxaline_1-1-dieq_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2419779 Zero-point correction= 0.576572 (Hartree/Particle) Thermal correction to Energy= 0.607645 Thermal correction to Enthalpy= 0.608590 Thermal correction to Gibbs Free Energy= 0.510900 Sum of electronic and ZPE= -1696.665406 Sum of electronic and thermal Energies= -1696.634332 Sum of electronic and thermal Enthalpies= -1696.633388 Sum of electronic and thermal Free Energies= -1696.731078 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.303 126.236 205.604 C,1.5852473834,-1.1708561515,-0.2567507058 C,3.0252837009,-3.2263406401,-0.4976839769 C,0.5582899163,-3.3269598111,-1.0124013299 C,1.77182647,-4.1038489439,-0.4934707796 C,0.3579615285,-2.0732136836,-0.1618212325 C,2.8022282804,-1.9309615443,0.2862450008 H,3.2862380548,-2.9764985921,-1.5345049882 H,0.7186392236,-3.0534879851,-2.0585989872 H,1.5742195002,-4.4510274627,0.5293442478 H,0.2975890152,-2.4183829639,0.884844052 H,2.6182373121,-2.1619060554,1.3446692366 H,1.751572804,-0.9652269526,-1.3262435572 H,3.8767656808,-3.7731010341,-0.0805666014 H,-0.3463639578,-3.9426092907,-0.9737999061 H,1.9284263623,-4.9963824684,-1.1072028375 H,3.6904435068,-1.2969259936,0.2399422086 N,-0.8680826447,-1.3033496849,-0.3904869229 N,1.3710512415,0.1071300548,0.4413856853 C,0.0744550135,0.54703716,0.9894733811 C,-1.09761559,-0.4678862262,0.7915262376 H,-1.0797992855,-1.1458756144,1.655842794 H,-0.2080555612,1.4635613874,0.4603001669 C,-2.4191440489,0.2743588716,0.84811728 C,-4.8369457828,1.6723648179,1.0732278325 C,-3.3655235159,-0.0921031477,1.8030419559 C,-2.6967730171,1.356019159,0.0056805026 C,-3.8971166085,2.0468658707,0.1129733109 328 C,-4.5693170542,0.6011241416,1.9178186229 H,-3.1533141523,-0.9219472579,2.4717344695 H,-1.9783024976,1.6485683465,-0.7556290333 H,-4.1009102946,2.8797840643,-0.5525679463 H,-5.2922258095,0.3053125497,2.6714346532 H,-5.771867295,2.216884893,1.1613431195 C,0.1658742098,0.8884829645,2.46973375 C,0.2181760853,1.4463546539,5.2137704078 C,0.9411892949,0.1151184372,3.3351260994 C,-0.58166718,1.9454041556,2.9919204034 C,-0.5565396145,2.2230801056,4.3560544239 C,0.968275272,0.3913157198,4.6992152678 H,1.5384345739,-0.6969581337,2.9285102649 H,-1.1867670367,2.5529421004,2.3235417116 H,-1.1391679,3.0510901939,4.7477996542 H,1.5797057512,-0.2149910005,5.3605955346 H,0.2421758471,1.6653719804,6.2766695316 H,-1.6452949006,-2.909176149,-5.3660570133 C,-2.4579730398,-2.3838266581,-4.877607957 C,-4.5775121071,-0.9929382487,-3.5634310132 C,-2.3398650363,-1.9288535446,-3.5807572848 C,-3.675448656,-2.1285515069,-5.5227864078 C,-4.7099748153,-1.4497507863,-4.8814000525 C,-3.374974564,-1.2513269792,-2.9391523596 H,-3.8123564132,-2.4673804833,-6.5442063521 H,-5.6392112061,-1.2699904133,-5.411591518 H,-5.3723856304,-0.4636212805,-3.050530471 O,-2.9847983321,-0.92428722,-1.6693953983 O,-1.2731445234,-2.0327153245,-2.7288418301 B,-1.6774081468,-1.4068142316,-1.5371374038 H,5.9808013824,1.9333431966,-1.4012507131 C,5.3407931361,2.6247917025,-0.8653066465 C,3.6307801192,4.4186304711,0.5516024287 C,4.127663409,2.2216045218,-0.3477441561 C,5.6958023399,3.9646879546,-0.6615415579 C,4.8609417073,4.8400764299,0.0303941727 C,3.2910640186,3.0978714738,0.344271715 H,6.641665571,4.3252664465,-1.051537533 H,5.1679140165,5.8710005932,0.1709105447 H,2.9730872028,5.0886641672,1.0931214386 O,2.1611849519,2.4323490061,0.7416405403 O,3.5438369272,0.9816751018,-0.4018338606 B,2.3280053375,1.1219407816,0.2800157264 329 P-Z,E[1,1]benzene (N,N-Diborylated product 2c from reductive coupling transition state TS-Z,E[1,1]benzene in benzene) trans-diax-diph-tetrahydroquinoxaline_1-1-dieq_benzene M062X/6-31G(d,p) E(RM062X) = -1697.258502 Zero-point correction= 0.577660 (Hartree/Particle) Thermal correction to Energy= 0.608371 Thermal correction to Enthalpy= 0.609316 Thermal correction to Gibbs Free Energy= 0.513639 Sum of electronic and ZPE= -1696.680842 Sum of electronic and thermal Energies= -1696.650131 Sum of electronic and thermal Enthalpies= -1696.649186 Sum of electronic and thermal Free Energies= -1696.744863 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.759 125.862 201.367 C,1.3948256093,-0.2194853079,-0.773320968 C,3.0187772076,-1.6815630394,-2.0228320649 C,0.6267593032,-2.4079308352,-1.7703259483 C,2.0795181981,-2.8742242258,-1.8566274504 C,0.4385149644,-1.418818945,-0.6217027055 C,2.8436967411,-0.6932501275,-0.8704560431 H,2.8023710515,-1.1793276727,-2.9749436503 H,0.3407581104,-1.9274605136,-2.7131827011 H,2.3458084427,-3.4210390493,-0.9424768846 H,0.7126157078,-1.9234905323,0.3188607226 H,3.1314925886,-1.1752973772,0.0710492909 H,1.128578424,0.2781688372,-1.7198608734 H,4.0606927265,-2.0135462834,-2.0669019411 H,-0.0454781769,-3.2594660849,-1.6323781331 H,2.1918445998,-3.5736392011,-2.6908603248 H,3.5022200129,0.1705358671,-0.9979910331 N,-0.9471365524,-0.9499704006,-0.4837673806 N,1.1741233713,0.7470502225,0.3111059375 C,-0.2152667624,1.2101647309,0.3956819903 C,-1.1287756258,-0.0092786028,0.6271506674 H,-2.1665059144,0.3302174559,0.606229097 H,-0.2922930177,1.8667714861,1.2648866896 C,-0.9316632517,-0.6931047555,1.9851819617 C,-0.7383176114,-2.0004262791,4.4709019146 C,-0.432828385,-0.0271638873,3.1079327565 C,-1.3363139812,-2.0241446236,2.1335657313 C,-1.242130611,-2.6727114548,3.3601852574 330 C,-0.3356644561,-0.676334761,4.3380358869 H,-0.1065939021,1.0049403143,3.0446567851 H,-1.723297635,-2.5599545208,1.2717371646 H,-1.562704841,-3.7063526022,3.4469017843 H,0.061879534,-0.1385232487,5.1932044951 H,-0.659795786,-2.504585564,5.428810364 C,-0.6018824956,2.0632935262,-0.8181658153 C,-1.2411352013,3.7689885556,-2.9646166849 C,0.3679322636,2.8891921969,-1.3967630214 C,-1.9004324451,2.1120435317,-1.332246667 C,-2.2153448274,2.9557480811,-2.3966749267 C,0.0552689275,3.7329486404,-2.4571516392 H,1.3838680161,2.8629205469,-1.0136433311 H,-2.6875691284,1.4918821781,-0.9181357205 H,-3.230198408,2.9696135124,-2.7820005713 H,0.8276570503,4.3627637319,-2.8877919969 H,-1.4878445969,4.4234049927,-3.7945590076 H,-3.3832622139,-3.3340382223,-4.5689321537 C,-3.9855531301,-2.7517437809,-3.8810947633 C,-5.5409020587,-1.2085572379,-2.0513565602 C,-3.4174651658,-2.1085783281,-2.8016208922 C,-5.3708925265,-2.6106271755,-4.0378818846 C,-6.1300756025,-1.8574501403,-3.1447473247 C,-4.1770726759,-1.3550674867,-1.9078955629 H,-5.8596895285,-3.09948678,-4.8738408368 H,-7.2007000923,-1.7697168717,-3.2960349727 H,-6.1202677881,-0.6207754887,-1.3485828571 O,-3.3566236198,-0.8382917434,-0.9408194427 O,-2.101261702,-2.0802199358,-2.4202274237 B,-2.0611625097,-1.2858992553,-1.2670598612 H,5.9681495553,1.0246330002,2.6018078279 C,5.185767562,1.6795933209,2.9676587347 C,3.101446738,3.3885773451,3.9075839766 C,3.9210759861,1.6587731865,2.4183216165 C,5.4000406284,2.5849610823,4.0155409413 C,4.3827005879,3.4191689141,4.474279209 C,2.9031741687,2.4935277244,2.8772194931 H,6.3802655788,2.6347886184,4.4775039776 H,4.5836061786,4.1086342729,5.2873574558 H,2.301737895,4.0330450492,4.2542393455 O,1.7653655261,2.260215972,2.1516928376 O,3.4466077429,0.8781914055,1.3964464 B,2.1049612381,1.2467840533,1.2337416977 331 P-E,E[1,2]benzene (N,N-Diborylated product 2b from reductive coupling transition state TS-E,E[1,2]benzene in benzene) cydiimph2_EE_b2cat2_1-2_product_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2112523 Zero-point correction= 0.577409 (Hartree/Particle) Thermal correction to Energy= 0.607315 Thermal correction to Enthalpy= 0.608259 Thermal correction to Gibbs Free Energy= 0.518636 Sum of electronic and ZPE= -1696.633843 Sum of electronic and thermal Energies= -1696.603937 Sum of electronic and thermal Enthalpies= -1696.602993 Sum of electronic and thermal Free Energies= -1696.692616 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.096 125.886 188.627 C,0.1337742327,2.7421994974,-0.4212639531 C,0.6325526741,5.1477845343,-0.1905560274 C,0.9470723289,3.5657307667,1.8075177418 C,0.6463167565,5.0016068561,1.3403960821 C,-0.062575352,2.6565027664,1.1168658671 C,-0.2834963406,4.1296953086,-0.8935898731 H,1.6536341824,5.0060898142,-0.5680804042 H,1.9690611564,3.2809709687,1.5420511239 H,-0.3336766507,5.2997767211,1.7362760824 H,-1.041999422,3.0994081637,1.3504869092 H,-1.3349924789,4.3283030267,-0.6450796722 H,1.203111526,2.6484079123,-0.6244976778 H,0.3382302714,6.1675055423,-0.4583455909 H,0.8478250084,3.4887480486,2.8953354188 H,1.3793297701,5.694133632,1.7660824944 H,-0.1816384039,4.2099506937,-1.9802600813 N,-0.5157188314,1.5643559355,-1.0242390231 N,-0.1831772747,1.2433852336,1.5144853909 C,-1.5570255596,0.8163831843,1.1580814522 H,-2.2206623566,1.4609181354,1.7501686026 C,-1.7967887644,1.2976615755,-0.3597259547 H,-2.252900367,2.287105023,-0.2387450114 B,0.9261356972,0.3728251664,1.3125494498 B,0.3725007983,0.4814207741,-1.294412049 O,1.6654173967,0.7302626257,-1.7359311237 O,0.8458510965,-0.9980153966,1.4861686832 C,3.0548065865,0.2992582371,0.1724878217 332 C,4.9107218533,-0.9446248121,-1.4780175427 C,2.8018596025,0.1811586866,-1.2031925449 C,4.2280870386,-0.2035624569,0.7140457319 C,5.1586431111,-0.8291996602,-0.1135979464 C,3.7336322561,-0.4378500889,-2.0249273241 H,4.3939396623,-0.0982323119,1.7811230843 H,6.07489131,-1.2249280454,0.311067592 H,3.5171227956,-0.5192011028,-3.0847801815 H,5.6332675836,-1.4313762523,-2.1243855024 O,2.133918048,0.9607791148,0.9461368711 C,1.1194829695,-1.9799333014,0.5823161975 C,1.5818913929,-4.0555447937,-1.2267414771 C,0.6558331237,-1.8896305886,-0.7394627824 C,1.8121011303,-3.1144948728,0.9863449715 C,2.0438884934,-4.1485915903,0.0826511597 C,0.8813104006,-2.9230599262,-1.6362711577 H,2.1590252524,-3.166909382,2.0127194168 H,2.58717404,-5.0295094819,0.4079963239 H,0.4975956619,-2.8235418249,-2.6463610914 H,1.7597315971,-4.8619845853,-1.9299125082 O,-0.0985043057,-0.8006059549,-1.0958283831 C,-1.8883759478,-0.5924161551,1.6408601408 C,-2.4548498738,-3.0845549925,2.8144830916 C,-1.9679793775,-0.7366791474,3.0321604547 C,-2.1178750371,-1.7165030017,0.8460483328 C,-2.3976973249,-2.9509377278,1.4321744303 C,-2.2399862593,-1.966118347,3.6178574268 H,-1.7915002281,0.1332655832,3.660685739 H,-2.0732560675,-1.6429916849,-0.2321523952 H,-2.5645401526,-3.8132163557,0.7938869493 H,-2.2867671572,-2.0515055004,4.6992070858 H,-2.6687602442,-4.0493051498,3.2639653883 C,-2.8218397941,0.5400144186,-1.179992637 C,-4.8362174366,-0.7517395168,-2.6494046691 C,-2.6035090592,0.1624236825,-2.5040699322 C,-4.0761170056,0.288411775,-0.61079452 C,-5.0724358454,-0.3552627687,-1.3340159519 C,-3.6019478729,-0.4845856034,-3.2312145298 H,-1.6532568144,0.3814835705,-2.9781060262 H,-4.2696196186,0.5870098453,0.4167225211 H,-6.034305466,-0.5487812725,-0.8695896096 H,-3.4103022602,-0.7760076154,-4.2593811326 H,-5.6114588544,-1.2575365518,-3.2160857423 333 P-E,Z[1,2]benzene (N,N-Diborylated product 2a from reductive coupling transition state TS-E,Z[1,2]benzene in benzene) cydiimph2_EZ_b2cat2_1-2_product_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2200978 Zero-point correction= 0.577755 (Hartree/Particle) Thermal correction to Energy= 0.607503 Thermal correction to Enthalpy= 0.608448 Thermal correction to Gibbs Free Energy= 0.519845 Sum of electronic and ZPE= -1696.642342 Sum of electronic and thermal Energies= -1696.612594 Sum of electronic and thermal Enthalpies= -1696.611650 Sum of electronic and thermal Free Energies= -1696.700253 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.214 125.898 186.480 C,-0.0757172914,2.3424739433,0.1338774397 C,-0.2565818206,4.6636815116,0.916549806 C,0.4071540373,2.7864480376,2.546058649 C,-0.2430259149,4.1725482554,2.3749915849 C,-0.308775754,1.8520956504,1.5793410679 C,-0.8516941369,3.6415273461,-0.0710700657 H,0.7739357593,4.8799432311,0.6060152642 H,1.4769346549,2.8289646683,2.3240645728 H,-1.2768188243,4.1191161532,2.7411554627 H,-1.3757810212,1.9819164392,1.8040902275 H,-1.9217724846,3.4987180247,0.1204497922 H,0.9784352306,2.6113874009,0.0515656146 H,-0.807555891,5.6075895145,0.8557074278 H,0.2891596909,2.4340361865,3.5760528545 H,0.273087738,4.9071409523,3.001190585 H,-0.7441706519,4.0036353354,-1.0990330973 N,-0.2539566091,1.2027752605,-0.7873907411 N,-0.0818021763,0.3924924016,1.6228452834 C,-1.2921200257,-0.1798239779,1.0148165328 H,-2.1255033991,0.2969709247,1.5420064762 C,-1.3794096344,0.3054720412,-0.4977277423 H,-1.2451902667,-0.5722386048,-1.1365600609 B,1.2011025011,-0.0553838616,1.1568102509 B,0.9143816778,0.6899143141,-1.4111517877 O,2.0560790544,1.4857653695,-1.4565111319 O,1.5430018399,-1.2905389185,0.646775922 C,3.3534786739,0.6866458071,0.406764763 334 C,5.5780212767,0.4959566675,-1.2579854038 C,3.2416870208,1.007629473,-0.9574719028 C,4.5731096137,0.271371676,0.9226858374 C,5.687380134,0.1776165371,0.0922406157 C,4.3555447318,0.9096758941,-1.7813525179 H,4.6301623314,0.0300416781,1.9789681221 H,6.637698525,-0.1460428219,0.5032087011 H,4.2432146053,1.1665536108,-2.8292780931 H,6.4428019947,0.4231578661,-1.9089372809 O,2.2635299377,0.8373191662,1.2346874913 C,1.0344374181,-2.1848868073,-0.2454500695 C,0.1146154379,-4.0773586424,-2.0757662898 C,0.7481154535,-1.8033161394,-1.5642970589 C,0.9154562029,-3.5195952082,0.1262704431 C,0.4526073266,-4.4645683525,-0.7812372638 C,0.2709272792,-2.7518634805,-2.4654382926 H,1.1719957105,-3.7886183407,1.1447806858 H,0.3470263257,-5.4985171875,-0.4703525522 H,0.0516702424,-2.4262396253,-3.4769073331 H,-0.2548836467,-4.806218991,-2.7892388114 O,1.0043879178,-0.5468514215,-2.023188299 C,-1.5029059573,-1.6618041876,1.2617797233 C,-2.0789523966,-4.3355986037,1.883391677 C,-2.2595692702,-2.4469754317,0.3887597525 C,-1.0493407274,-2.2279606355,2.4574397418 C,-1.3315436838,-3.5552713263,2.7634971736 C,-2.5437619877,-3.7754266131,0.6976248897 H,-2.6357105817,-2.0308568736,-0.54199562 H,-0.4721042463,-1.6169477268,3.1443630855 H,-0.9683021793,-3.9808429215,3.6941943384 H,-3.1247311405,-4.3733183948,0.0022537194 H,-2.2987871645,-5.37151097,2.1218689784 C,-2.7264789558,0.9092156769,-0.8798343003 C,-5.199240333,1.9600202459,-1.7053820297 C,-2.8048773344,1.7937548593,-1.9609467022 C,-3.9103450876,0.5448869248,-0.2319692756 C,-5.1365963247,1.0675637009,-0.6411212382 C,-4.0264493752,2.3187233177,-2.3673185285 H,-1.891590492,2.077372816,-2.4747960892 H,-3.8934903542,-0.1633585732,0.5916196576 H,-6.0431369952,0.773114953,-0.1216210829 H,-4.0626202963,3.0100233032,-3.2036704908 H,-6.153377911,2.3702465029,-2.020435058 335 P-Z,E[1,2]benzene (N,N-Diborylated product 2c from reductive coupling transition state TS-Z,E[1,2]benzene in benzene) cydiimph2_ZE_b2cat2_1-2_product_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2262009 Zero-point correction= 0.577557 (Hartree/Particle) Thermal correction to Energy= 0.607421 Thermal correction to Enthalpy= 0.608365 Thermal correction to Gibbs Free Energy= 0.518879 Sum of electronic and ZPE= -1696.648644 Sum of electronic and thermal Energies= -1696.618780 Sum of electronic and thermal Enthalpies= -1696.617836 Sum of electronic and thermal Free Energies= -1696.707322 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.162 125.894 188.340 C,-0.4226802431,1.8240805523,1.4084276446 C,-0.4605363138,4.093131693,2.3579520197 C,-0.4247412745,3.7502278179,-0.1917822888 C,-0.0667052058,4.673170372,0.9880428837 C,0.1965545611,2.3951298219,0.1124135765 C,0.054537351,2.6599208435,2.5902103772 H,-1.5554533593,4.0772898913,2.4345641727 H,-1.5096903526,3.6613662779,-0.3038019463 H,1.0173219785,4.8471944925,0.9736938963 H,1.2567206299,2.6074583179,0.306876891 H,1.1507487489,2.6554608985,2.6597853498 H,-1.5027475773,1.9580636585,1.3472192452 H,-0.1002727871,4.7553862992,3.151519036 H,-0.019885523,4.1524917712,-1.126505309 H,-0.5424940768,5.6502283862,0.8574580574 H,-0.3402248516,2.2612809427,3.5301614845 N,-0.1815618458,0.3682602377,1.4243035786 N,0.2020688664,1.3277632283,-0.903294579 C,1.3210981884,0.4371398216,-0.5569962991 H,1.2239732883,-0.4823267652,-1.1377943861 C,1.188177036,0.072221148,0.982133968 H,1.8285647213,0.7794377,1.5268395828 B,-1.0428597304,0.708896262,-1.2276759705 B,-1.3129433054,-0.4613776372,1.1739353902 O,-2.572854781,0.0739369203,1.4414613517 O,-1.2144023239,-0.5435570737,-1.7865536786 C,-3.3859492994,0.7082202267,-0.7336752182 336 C,-5.7847685797,-0.5961304412,-0.1876540062 C,-3.5565230323,0.0308519059,0.4868406997 C,-4.4126694628,0.7242336064,-1.667106709 C,-5.6141202042,0.0740256847,-1.3951771662 C,-4.7560941869,-0.6177054905,0.7509106914 H,-4.2530106697,1.2555901689,-2.5995317722 H,-6.4128513714,0.0924461652,-2.1289827771 H,-4.8637875697,-1.1300682595,1.7010123609 H,-6.7183005225,-1.1048810942,0.0283443502 O,-2.2189089528,1.400666477,-0.9716544839 C,-0.617698075,-1.7528869964,-1.579722356 C,0.4233752979,-4.3116129247,-1.2216060522 C,-0.6822365843,-2.3672264076,-0.320022033 C,-0.0221339236,-2.4189335502,-2.6460929985 C,0.5043042341,-3.6949615423,-2.4676130718 C,-0.1725594129,-3.6497226166,-0.1536114118 H,0.0086752217,-1.9198526689,-3.608983836 H,0.9678442298,-4.2057493115,-3.3047777991 H,-0.2328099173,-4.0978124238,0.8328433569 H,0.8298726086,-5.3066284876,-1.0742973143 O,-1.3166552146,-1.7666013273,0.7221584892 C,2.6585730522,1.0679303729,-0.9383371347 C,5.0886443191,2.2139327582,-1.7627548681 C,2.7428924798,1.7865432146,-2.1364757569 C,3.8112801951,0.9354169153,-0.1596561766 C,5.0170177803,1.5037946222,-0.569830683 C,3.9443386865,2.3530775198,-2.5462981871 H,1.8468668704,1.9069623821,-2.737435753 H,3.7872783104,0.3777471913,0.7717878486 H,5.900030289,1.3896581166,0.0511497206 H,3.9871297921,2.9078728474,-3.4785374777 H,6.0269523623,2.6576477269,-2.0801232016 C,1.6719575866,-1.3149356921,1.3718483684 C,2.6348729779,-3.8200054129,2.2007946112 C,1.2663419523,-1.8691977249,2.5911517841 C,2.5700340109,-2.0326255348,0.5783800391 C,3.051239127,-3.2733720427,0.9920730266 C,1.7379913481,-3.1119406276,2.9996034775 H,0.5715729364,-1.3191373132,3.2184118858 H,2.8975565081,-1.6371989403,-0.3785680715 H,3.7432909819,-3.8161577614,0.3557939375 H,1.406474448,-3.5270141649,3.9464685799 H,3.0046115543,-4.7892080233,2.5204490396 337 P-Z,Z[1,2]benzene (N,N-Diborylated product 2b from reductive coupling transition state TS-Z,Z[1,2]benzene in benzene) cydiimph2_ZZ_b2cat2_1-2_product_benzene M062X/6-31G(d,p) E(RM062X) = -1697.2160513 Zero-point correction= 0.577649 (Hartree/Particle) Thermal correction to Energy= 0.607606 Thermal correction to Enthalpy= 0.608550 Thermal correction to Gibbs Free Energy= 0.518402 Sum of electronic and ZPE= -1696.638403 Sum of electronic and thermal Energies= -1696.608446 Sum of electronic and thermal Enthalpies= -1696.607501 Sum of electronic and thermal Free Energies= -1696.697649 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 381.278 125.922 189.732 C,-0.0130981234,-1.9070549766,0.3354515653 C,-0.5728816583,-4.2742890873,-0.0292771124 C,-0.2209047343,-2.7046534706,-2.027219737 C,-0.9352937244,-3.9569436647,-1.4893445139 C,-0.5328898703,-1.5596753059,-1.0735309034 C,-0.8018060846,-3.0803932592,0.9141608101 H,0.4854070796,-4.5629654817,0.0196066126 H,0.8596619788,-2.8697789983,-2.0809567825 H,-2.0199582088,-3.797600249,-1.5592269451 H,-1.6273527175,-1.500615185,-1.0309541444 H,-1.8704162373,-2.8550914273,0.9850159734 H,1.0077742938,-2.2725409166,0.2176234442 H,-1.1514358846,-5.1384731063,0.3122813521 H,-0.5731169213,-2.4672110037,-3.0372584415 H,-0.7030297206,-4.8191090006,-2.1225467199 H,-0.4449122021,-3.3128343069,1.9229657969 N,0.0987628876,-0.6459374588,1.0927295278 N,-0.0781904284,-0.1931008522,-1.4043927754 C,-0.9550170111,0.7367604894,-0.6846007681 H,-0.4660597329,1.7088313667,-0.6683593596 C,-1.0132105123,0.2925628664,0.8576344327 H,-0.7797974709,1.19373217,1.4321693278 B,1.3235096066,0.074528218,-1.2836244538 B,1.4057699658,-0.1882242213,1.3982876152 O,2.4493093634,-1.1089997015,1.3793048696 O,1.9200439307,1.2987550827,-1.0260226354 C,3.4623414175,-0.870116295,-0.7960732631 338 C,5.9658833271,-0.7630448362,0.4200659923 C,3.5658918553,-0.9200441688,0.6058518857 C,4.6081740277,-0.7659224273,-1.5717723564 C,5.8616115921,-0.7154172891,-0.9664604621 C,4.8189042388,-0.8654891429,1.2032422773 H,4.4966102714,-0.729323284,-2.650399928 H,6.7521715523,-0.6366052108,-1.5807860656 H,4.8719633775,-0.9113963397,2.2857661707 H,6.9391600391,-0.7223477122,0.8975006886 O,2.2278392922,-0.970646013,-1.4012903445 C,1.5674534493,2.3863072505,-0.2827076419 C,0.9526377045,4.6377938746,1.2399941905 C,1.4644867845,2.2806418026,1.1145518666 C,1.379637416,3.6177463699,-0.9012277197 C,1.0691267032,4.7430554192,-0.14330484 C,1.1535677223,3.4106525601,1.8650151459 H,1.4758915466,3.6678752378,-1.9807079285 H,0.9200513736,5.69750218,-0.6362397971 H,1.0837772222,3.3032799681,2.9424756028 H,0.7111274921,5.5101522444,1.8376556652 O,1.7305309462,1.1122128474,1.7588614244 C,-2.272769076,1.0142945181,-1.3829472399 C,-4.7085608403,1.6207334908,-2.6292523203 C,-2.6065694326,0.4291118603,-2.6034250485 C,-3.1564397821,1.935596037,-0.810036196 C,-4.3662191394,2.2344355577,-1.4244433651 C,-3.8230925844,0.7245560475,-3.2186769446 H,-1.9056713191,-0.2535400468,-3.0740359011 H,-2.8971198873,2.4111594256,0.1333699403 H,-5.0439311109,2.9462741715,-0.9636916743 H,-4.0736067465,0.255063713,-4.1650453004 H,-5.6548735575,1.8498102527,-3.1088324268 C,-2.2955259427,-0.256553393,1.4925552465 C,-4.4619319541,-1.3304579955,2.9377379662 C,-2.2839667592,-0.3044420044,2.8926151951 C,-3.4206311036,-0.7542072041,0.8298126988 C,-4.4919863059,-1.2855238177,1.5488681837 C,-3.3476774502,-0.8347980674,3.6115959322 H,-1.4104658558,0.069443109,3.4219234739 H,-3.4849107252,-0.7418647802,-0.2510170281 H,-5.3537305135,-1.6668779703,1.0100234501 H,-3.3069908877,-0.8612020905,4.6960355521 H,-5.2980622409,-1.7458973683,3.4912592076 2aMeOH (Diamine product 2a in MeOH) trans-dieq-diph-tetrahydroquinoxaline_meoh 339 M062X/6-31G(d,p) E(RM062X) = -885.7669331 Zero-point correction= 0.406107 (Hartree/Particle) Thermal correction to Energy= 0.423922 Thermal correction to Enthalpy= 0.424866 Thermal correction to Gibbs Free Energy= 0.360073 Sum of electronic and ZPE= -885.360826 Sum of electronic and thermal Energies= -885.343011 Sum of electronic and thermal Enthalpies= -885.342067 Sum of electronic and thermal Free Energies= -885.406860 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.015 73.669 136.368 H,1.5186467414,-3.4442180063,-1.9267503953 C,1.8453808493,-3.1097018078,-0.9348171296 C,3.833239866,-2.7635381677,0.5830397315 C,1.8970361792,-1.1570472596,0.6409724935 C,3.4064983574,-1.3093134832,0.7943714661 C,1.4428830564,-1.6532142848,-0.7302885557 C,3.356960533,-3.2864116235,-0.7753199477 H,3.4027318005,-3.3854381629,1.3792633482 H,1.3953173589,-1.7968229414,1.3929912494 H,3.8996050486,-0.6634286388,0.0557461278 H,1.9639010537,-1.0296772397,-1.4828234098 H,3.8711300008,-2.7349056723,-1.5737808362 H,1.3164587109,-3.7254509611,-0.1952340152 H,4.9216125052,-2.8513191444,0.6641808954 H,3.7112969581,-0.9563403975,1.7868913307 H,3.6264222301,-4.3411342079,-0.8927722945 N,-0.0071522975,-1.4955699062,-0.8255840644 H,-0.3198565911,-1.8374401283,-1.7333615496 N,1.4975542142,0.2415218603,0.7857277633 H,1.8093532067,0.5841538173,1.693529458 C,0.0463918027,0.4062515004,0.7007186617 H,-0.4826103621,-0.2174812169,1.4437720338 C,-0.4141263961,-0.0968337221,-0.6908847076 H,0.0867207485,0.5505890802,-1.4331851586 C,-0.3420561693,1.8511729511,0.9161800294 C,-1.1391475613,4.5227146646,1.218843144 C,0.4000764616,2.883598338,0.3348426211 C,-1.4858096549,2.1728912632,1.6513095799 C,-1.8843503528,3.4991706697,1.8018569768 C,0.004352,4.2111139419,0.4853159535 340 H,1.2931278187,2.639060991,-0.2324072924 H,-2.0717131216,1.3744957741,2.1010639095 H,-2.7754106577,3.7334041055,2.3767251882 H,0.5904764741,5.0035602293,0.0291907954 H,-1.4470333695,5.5572938404,1.336629745 C,-1.9101445238,0.0438647899,-0.8559517146 C,-4.6866122747,0.3791729824,-1.0630507707 C,-2.4449941449,1.1345500205,-1.5461920891 C,-2.782224798,-0.8792205684,-0.2711392486 C,-4.1618205415,-0.7129533137,-0.374136998 C,-3.8238548423,1.3038046193,-1.6492082478 H,-1.7726481958,1.8602114201,-1.9982580621 H,-2.3713831828,-1.7317996547,0.261241981 H,-4.8280702487,-1.4379809465,0.0841308678 H,-4.2244475332,2.1563887046,-2.1895350965 H,-5.7617075374,0.5082562329,-1.1438537152 2bMeOH (Diamine product 2b in MeOH) cis-diph-tetrahydroquinoxaline_meoh M062X/6-31G(d,p) E(RM062X) = -885.7574577 Zero-point correction= 0.406964 (Hartree/Particle) Thermal correction to Energy= 0.424653 Thermal correction to Enthalpy= 0.425597 Thermal correction to Gibbs Free Energy= 0.360397 Sum of electronic and ZPE= -885.350494 Sum of electronic and thermal Energies= -885.332805 Sum of electronic and thermal Enthalpies= -885.331861 Sum of electronic and thermal Free Energies= -885.397060 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.474 73.565 137.224 H,2.3030813076,-2.9870584036,1.516714549 C,2.6314738075,-1.9896349436,1.2055124398 C,4.5733303959,-0.6141818157,0.3482491764 C,2.2390090923,-0.1439786962,-0.4556706081 C,3.7163818765,-0.1527627185,-0.8325500499 C,1.7907172416,-1.5265876031,0.0208711515 C,4.1213676993,-1.9871871228,0.8538155422 H,4.4878485572,0.1166703346,1.1635374521 H,2.0994032127,0.5524727251,0.3954028702 H,3.855461464,-0.8332240172,-1.6836409475 H,1.942134511,-2.2215304408,-0.820166369 341 H,4.3053058207,-2.7357821022,0.0715609916 H,2.4525397973,-1.3108906477,2.0522312789 H,5.6288248296,-0.6451479421,0.0584602258 H,4.0193726482,0.8475049715,-1.1655109608 H,4.7138495494,-2.285379362,1.7250580541 N,0.3647109184,-1.5569769938,0.3543405391 H,0.2277649815,-0.9890176953,1.1908596056 N,1.4127353417,0.2286931835,-1.6026460808 H,1.7380658283,1.1224332264,-1.9674567331 C,-0.0151590548,0.3487024168,-1.2573994484 H,-0.533571761,0.5266013399,-2.206556263 C,-0.4669611358,-1.0349507857,-0.7350272215 H,-0.2894193645,-1.7100785281,-1.5851094795 C,-0.3086546205,1.5581068494,-0.3643544055 C,-0.7205619923,3.9060111483,1.1428498648 C,-0.8092052059,1.4967634057,0.939919581 C,-0.0318902666,2.8241464834,-0.8996573753 C,-0.2333109577,3.9853701968,-0.1614145803 C,-1.0103164086,2.6590111464,1.6866945716 H,-1.0764785938,0.5456199302,1.3878859918 H,0.3396296951,2.9006025148,-1.9199490094 H,-0.0150163424,4.952333131,-0.6048753763 H,-1.3989592117,2.5826645271,2.6978675043 H,-0.8796330748,4.8086428166,1.724794766 C,-1.9488013881,-1.1236642562,-0.3961080079 C,-4.6929682666,-1.3410748587,0.1949608164 C,-2.3969816916,-1.9548545524,0.6352509949 C,-2.9010080441,-0.4057689143,-1.1304050843 C,-4.2582510157,-0.5140168841,-0.8391294586 C,-3.7554766997,-2.0614042774,0.929718598 H,-1.6727212526,-2.5215237682,1.2098719947 H,-2.5899692507,0.2481440032,-1.9395777884 H,-4.9778510979,0.0540438847,-1.4213073703 H,-4.0789683163,-2.7111871453,1.7376856858 H,-5.751056602,-1.4218747806,0.424393362 2cMeOH (Diamine product 2c in MeOH) trans-diax-diph-tetrahydroquinoxaline_meoh M062X/6-31G(d,p) E(RM062X) = -885.7582061 Zero-point correction= 0.406868 (Hartree/Particle) Thermal correction to Energy= 0.424571 Thermal correction to Enthalpy= 0.425515 Thermal correction to Gibbs Free Energy= 0.360597 Sum of electronic and ZPE= -885.351338 342 Sum of electronic and thermal Energies= -885.333636 Sum of electronic and thermal Enthalpies= -885.332691 Sum of electronic and thermal Free Energies= -885.397609 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.422 73.419 136.631 H,2.0997341173,1.2553246072,-2.5725217141 C,2.1855996254,1.2965804375,-1.4799622129 C,2.6772389105,2.7743355838,0.5053129099 C,0.940379598,0.9588969723,0.673492395 C,1.3471134523,2.3550169558,1.1346520149 C,0.8553102376,0.8972221572,-0.8490147189 C,2.6120460127,2.6929465343,-1.0223217888 H,3.4739082451,2.1108257879,0.8674779392 H,1.7256110546,0.2423434138,0.9826229662 H,0.5575495481,3.0612931517,0.844590862 H,0.0838880022,1.6280496504,-1.1594950925 H,1.887976087,3.4314988844,-1.3915831535 H,2.9451659507,0.5592971718,-1.1869689029 H,2.9397273175,3.7891056166,0.8220180126 H,1.4120781335,2.374668596,2.229254498 H,3.5819505058,2.9520423952,-1.4594889358 N,0.5013750032,-0.4683441213,-1.2323942816 H,0.4535971084,-0.5247660892,-2.2491178757 N,-0.3688122471,0.6053679337,1.2194367436 H,-0.3274996959,0.6551069836,2.2367923021 C,-0.8129535427,-0.7496635811,0.8438717628 H,-1.8609642081,-0.8282231038,1.1574149334 C,-0.7946858006,-0.9120767039,-0.6867307046 H,-0.8630045722,-1.9874137963,-0.8911566237 C,-0.0546063039,-1.8400217746,1.5966321132 C,1.2963793584,-3.7641469121,3.1401310693 C,1.0313382537,-2.5449278798,1.0666893614 C,-0.4514180378,-2.1177732319,2.9105469819 C,0.2149275703,-3.0681741259,3.6787481359 C,1.6993964529,-3.4998399306,1.8336051247 H,1.3560388093,-2.3353725613,0.0525600617 H,-1.3006411562,-1.5828307054,3.3316075252 H,-0.1141282952,-3.2713313192,4.6936294834 H,2.5400337337,-4.0384603582,1.4057372933 H,1.8179412316,-4.5087986533,3.7338172177 C,-1.9787169363,-0.2617276972,-1.3978819606 C,-4.0888610639,0.8776914616,-2.8671758636 C,-2.6708998689,0.8501910614,-0.9064280141 343 C,-2.3637569623,-0.7921391973,-2.635373587 C,-3.4065501916,-0.2308542949,-3.3667783183 C,-3.7181244053,1.4131769132,-1.6362816098 H,-2.3792019354,1.277777528,0.0474505149 H,-1.8393047916,-1.6627819972,-3.0246889196 H,-3.6917901913,-0.6626655043,-4.3216144191 H,-4.2452729016,2.275835779,-1.2390561976 H,-4.9051112345,1.3177379335,-3.432057274 2aDMF (Diamine product 2a in DMF) trans-dieq-diph-tetrahydroquinoxaline_dmf M062X/6-31G(d,p) E(RM062X) = -885.7655681 Zero-point correction= 0.406098 (Hartree/Particle) Thermal correction to Energy= 0.423871 Thermal correction to Enthalpy= 0.424815 Thermal correction to Gibbs Free Energy= 0.360391 Sum of electronic and ZPE= -885.359470 Sum of electronic and thermal Energies= -885.341697 Sum of electronic and thermal Enthalpies= -885.340753 Sum of electronic and thermal Free Energies= -885.405177 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 265.983 73.671 135.592 H,1.5155424088,-3.4395319702,-1.9287322822 C,1.8416126041,-3.1057032845,-0.9364716267 C,3.8291843844,-2.7603092737,0.5833262278 C,1.8923984706,-1.155869276,0.642213671 C,3.4019697236,-1.3063308796,0.7962478382 C,1.4408934021,-1.6488158991,-0.7313525043 C,3.3530801548,-3.2829631579,-0.7753942233 H,3.3983835089,-3.3825238262,1.3790084027 H,1.3891090551,-1.7980771501,1.3912772408 H,3.8932219016,-0.6584978866,0.0581309786 H,1.9641315166,-1.0233931799,-1.4809495419 H,3.867526447,-2.7311291989,-1.5733132426 H,1.3104397263,-3.7199463612,-0.1972872084 H,4.9174350642,-2.8481982131,0.6643355094 H,3.7062146517,-0.9541380644,1.7890921446 H,3.6226315164,-4.3375506062,-0.8927138242 N,-0.0080743015,-1.4896967118,-0.8263556493 H,-0.3254291275,-1.838137508,-1.7299032026 N,1.4916368859,0.2414033898,0.7866822455 344 H,1.8089817567,0.5898525624,1.690230065 C,0.0416140832,0.4099502575,0.7016124492 H,-0.491086984,-0.2121152044,1.4436244951 C,-0.4186116635,-0.0927384535,-0.6915307844 H,0.0799954562,0.5580142018,-1.4326310905 C,-0.3390171511,1.857407601,0.914898569 C,-1.1140914608,4.5353911437,1.2130379655 C,0.4235125845,2.8839065749,0.3496663841 C,-1.491743837,2.1877734493,1.6319179591 C,-1.8792750156,3.5175567791,1.7802667577 C,0.0384071468,4.2148793198,0.4975878576 H,1.324016165,2.6296871038,-0.2014741323 H,-2.0926087906,1.3934878692,2.0689540224 H,-2.7771511139,3.7591212989,2.3411043343 H,0.6399086008,5.0029535957,0.0543184401 H,-1.4135058594,5.5725093075,1.3293177899 C,-1.9157265892,0.0397699005,-0.854602248 C,-4.6946435218,0.3521715189,-1.0577008706 C,-2.4600557643,1.1373340381,-1.5262389988 C,-2.7789969035,-0.9019643367,-0.2866760603 C,-4.1601072174,-0.746814856,-0.3873654219 C,-3.8404215907,1.2950875674,-1.6273107256 H,-1.7939101006,1.8766913831,-1.9650207978 H,-2.3578534817,-1.7597998242,0.2291209942 H,-4.8198319725,-1.4858991138,0.0574610021 H,-4.2489572019,2.1527587868,-2.1532122622 H,-5.770747944,0.4724369247,-1.1371965939 2bDMF (Diamine product 2b in DMF) cis-diph-tetrahydroquinoxaline_dmf M062X/6-31G(d,p) E(RM062X) = -885.755629 Zero-point correction= 0.406775 (Hartree/Particle) Thermal correction to Energy= 0.424478 Thermal correction to Enthalpy= 0.425422 Thermal correction to Gibbs Free Energy= 0.360055 Sum of electronic and ZPE= -885.348854 Sum of electronic and thermal Energies= -885.331151 Sum of electronic and thermal Enthalpies= -885.330207 Sum of electronic and thermal Free Energies= -885.395574 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.364 73.632 137.576 345 H,2.2925097271,-2.9746117906,1.5336736437 C,2.6271002161,-1.9812760243,1.2162008701 C,4.5740957277,-0.6215137363,0.3446535788 C,2.2400692789,-0.1403664724,-0.4528147622 C,3.7160785304,-0.1598038206,-0.8354536162 C,1.7869384926,-1.5198860898,0.0306791168 C,4.1158169968,-1.989353524,0.8592251247 H,4.4954911685,0.1137576136,1.1565301087 H,2.1060915535,0.5601534707,0.3960705229 H,3.8458235161,-0.8451572147,-1.6840613481 H,1.9347214158,-2.2178131043,-0.8087375964 H,4.2920588401,-2.7428283631,0.0800135365 H,2.4543842746,-1.29621486,2.0589850341 H,5.6283141912,-0.6604135768,0.0516549006 H,4.0242661212,0.8367652137,-1.1743104733 H,4.7100584686,-2.2862593792,1.729555067 N,0.3617302308,-1.5422720862,0.3642238572 H,0.2240827976,-0.9722977514,1.1990162871 N,1.4120419716,0.2281756799,-1.5988878396 H,1.7411536573,1.1131759716,-1.9806693403 C,-0.0157305994,0.3529567549,-1.2580402819 H,-0.5321569963,0.5280105599,-2.2091271 C,-0.4682941263,-1.0287219717,-0.7298323002 H,-0.2844125689,-1.7075357447,-1.5757858044 C,-0.3080570054,1.5660304553,-0.3686389234 C,-0.716546331,3.9183258926,1.1323200732 C,-0.8129960624,1.508975985,0.9341194992 C,-0.0245077086,2.8298220266,-0.9056408014 C,-0.224482423,3.9933007991,-0.1704803423 C,-1.0124034133,2.6734797148,1.6779351115 H,-1.0846748538,0.5594572958,1.3828572665 H,0.3516646798,2.9022066129,-1.9244194454 H,-0.0010779081,4.9584985858,-0.6149835272 H,-1.4043698923,2.6006225185,2.6879635728 H,-0.8743284656,4.8226273475,1.71181627 C,-1.9500808598,-1.1235954039,-0.3928858925 C,-4.6922441427,-1.3644394989,0.1948300251 C,-2.3948069861,-1.9881790875,0.6124876576 C,-2.903842505,-0.3832657231,-1.1020471368 C,-4.2606415441,-0.5033067254,-0.8124116714 C,-3.7525555781,-2.1064594333,0.9052945212 H,-1.6663720808,-2.56996228,1.1666820347 H,-2.5939926862,0.2983678867,-1.8883775156 H,-4.9821031472,0.0822642944,-1.3743806807 H,-4.0742189044,-2.7822007524,1.6922860978 H,-5.7497781077,-1.4544412844,0.4229076115 346 2cDMF (Diamine product 2c in DMF) trans-diax-diph-tetrahydroquinoxaline_dmf M062X/6-31G(d,p) E(RM062X) = -885.7571777 Zero-point correction= 0.406770 (Hartree/Particle) Thermal correction to Energy= 0.424476 Thermal correction to Enthalpy= 0.425420 Thermal correction to Gibbs Free Energy= 0.360502 Sum of electronic and ZPE= -885.350407 Sum of electronic and thermal Energies= -885.332702 Sum of electronic and thermal Enthalpies= -885.331758 Sum of electronic and thermal Free Energies= -885.396676 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.362 73.467 136.631 H,2.1118907109,1.2354347051,-2.5665995605 C,2.1901837724,1.2836998256,-1.4738746546 C,2.6671927514,2.7758029486,0.5057358912 C,0.9340734845,0.9585910259,0.6741493736 C,1.3335543264,2.3586205591,1.129441729 C,0.8551807401,0.8908759187,-0.8490426393 C,2.6138430927,2.682952489,-1.0219384519 H,3.4619161347,2.1159928412,0.8784898298 H,1.7207824356,0.245875294,0.9886907001 H,0.5433776687,3.0599206568,0.8292150319 H,0.087012108,1.6227558961,-1.1653962163 H,1.8925306829,3.4186440263,-1.4018680533 H,2.9457789412,0.5466544885,-1.1702677393 H,2.9260410228,3.7932126763,0.8164775395 H,1.3912771153,2.3856231677,2.2241773062 H,3.5870713563,2.9390816434,-1.4531112208 N,0.4998285938,-0.474999993,-1.2264413531 H,0.4656110869,-0.5448655024,-2.2427707985 N,-0.3759358867,0.6030619882,1.2143312817 H,-0.348543771,0.6658724156,2.2313278849 C,-0.8168354109,-0.7537187093,0.8443189263 H,-1.8639586996,-0.8335484893,1.160445893 C,-0.7986164467,-0.916097,-0.6864142224 H,-0.8684753259,-1.990838532,-0.8933601355 C,-0.0528794076,-1.841272256,1.5961845724 C,1.3071828812,-3.7609174558,3.1369173205 C,1.0325761931,-2.5446897053,1.0628044368 347 C,-0.444063141,-2.1176696713,2.9119888275 C,0.2267979361,-3.0659392248,3.6789115464 C,1.7049392695,-3.4975592693,1.8285393457 H,1.3533093701,-2.3341954457,0.0473885135 H,-1.2923349758,-1.5831418111,3.3352691322 H,-0.0978354919,-3.268201563,4.6952775665 H,2.5449331115,-4.0352328275,1.3984809661 H,1.8321800314,-4.5038818487,3.7295044358 C,-1.9799836972,-0.2600015957,-1.3974793964 C,-4.0857513542,0.8888434516,-2.8653220841 C,-2.6703438967,0.8518071679,-0.902718438 C,-2.3640656257,-0.7849594018,-2.6375041769 C,-3.404787679,-0.2189975384,-3.3682742945 C,-3.71558693,1.4192484651,-1.6320056508 H,-2.3774419036,1.2755983821,0.0527168192 H,-1.8402705228,-1.6548834186,-3.0290680295 H,-3.6894430844,-0.6465280724,-4.3250844876 H,-4.2415631949,2.2815070493,-1.232641378 H,-4.9003483933,1.3324622209,-3.4296018352 2abenzene (Diamine product 2a in benzene) trans-dieq-diph-tetrahydroquinoxaline_benzene M062X/6-31G(d,p) E(RM062X) = -885.7652427 Zero-point correction= 0.406833 (Hartree/Particle) Thermal correction to Energy= 0.424553 Thermal correction to Enthalpy= 0.425497 Thermal correction to Gibbs Free Energy= 0.361219 Sum of electronic and ZPE= -885.358410 Sum of electronic and thermal Energies= -885.340690 Sum of electronic and thermal Enthalpies= -885.339746 Sum of electronic and thermal Free Energies= -885.404024 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.411 73.517 135.286 H,1.5118710097,-3.4341216618,-1.9307759498 C,1.8349798797,-3.099119643,-0.9377177384 C,3.8226507333,-2.7546225257,0.5835510104 C,1.8846982022,-1.1513468565,0.6432572188 C,3.3943939733,-1.3009592828,0.7978739127 C,1.4350940066,-1.6419794852,-0.7320350443 C,3.3463585717,-3.2774967395,-0.7752645347 H,3.3932623354,-3.3780479753,1.3789625705 348 H,1.3788508257,-1.7968022482,1.3882651229 H,3.8840147143,-0.6488711522,0.0630636556 H,1.9612213393,-1.0135879735,-1.4775852747 H,3.8622467063,-2.726853554,-1.5729892693 H,1.2992346404,-3.7123978818,-0.2016740208 H,4.9107336967,-2.8428410017,0.664451318 H,3.7003242946,-0.951502958,1.7913915125 H,3.6162093001,-4.3318654239,-0.8924786823 N,-0.011380271,-1.4813078853,-0.8220573537 H,-0.3451544451,-1.8454284991,-1.7123873613 N,1.4826768851,0.2433353471,0.7827119662 H,1.8122512872,0.6109897164,1.6731542841 C,0.0346908967,0.4211992738,0.7001954114 H,-0.5031272342,-0.1949619342,1.4439635664 C,-0.430826339,-0.0878845663,-0.6896019622 H,0.0610385564,0.5669424302,-1.4321412366 C,-0.3294545855,1.8745555357,0.9060849293 C,-1.0624723737,4.5633551495,1.1920798323 C,0.480902009,2.8888866572,0.3887433348 C,-1.5090685825,2.2223134039,1.5677765004 C,-1.8753349746,3.5574610807,1.710068407 C,0.1162154411,4.2255268861,0.5315265851 H,1.4014469289,2.6158327812,-0.118234242 H,-2.1500652097,1.4367713653,1.9606845443 H,-2.7959166282,3.8123209975,2.2259199525 H,0.7548877705,5.0049359145,0.1268433011 H,-1.3457119852,5.6053443911,1.3042963854 C,-1.930708828,0.0271821658,-0.8456436755 C,-4.712728047,0.2959909955,-1.0376395181 C,-2.4950187815,1.1467898446,-1.4606992618 C,-2.775340821,-0.9583090864,-0.3273854889 C,-4.1583909262,-0.8243756824,-0.4234307945 C,-3.8768528807,1.2825219232,-1.5562434944 H,-1.8429448336,1.9230112481,-1.8539035351 H,-2.3336137195,-1.8314927108,0.1431622324 H,-4.8044523737,-1.5975673885,-0.0185499108 H,-4.3009454464,2.1590924342,-2.0361357846 H,-5.7907451011,0.3993849176,-1.1134533684 2bbenzene (Diamine product 2b in benzene) cis-diph-tetrahydroquinoxaline_benzene M062X/6-31G(d,p) E(RM062X) = -885.7540926 Zero-point correction= 0.407405 (Hartree/Particle) Thermal correction to Energy= 0.425004 349 Thermal correction to Enthalpy= 0.425948 Thermal correction to Gibbs Free Energy= 0.361612 Sum of electronic and ZPE= -885.346688 Sum of electronic and thermal Energies= -885.329089 Sum of electronic and thermal Enthalpies= -885.328145 Sum of electronic and thermal Free Energies= -885.392481 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.694 73.504 135.406 H,2.2700610304,-2.9279903813,1.5876541199 C,2.6146037031,-1.9459858371,1.2483274324 C,4.5693768921,-0.6220505192,0.3372059226 C,2.2344386988,-0.1350866107,-0.4556783452 C,3.7079870058,-0.1753938126,-0.846666446 C,1.7737197248,-1.5021315141,0.0567316833 C,4.1015605905,-1.9742971361,0.8843354708 H,4.5045651722,0.1308347536,1.1339947039 H,2.111002644,0.5839289927,0.3797318347 H,3.8239332757,-0.8753228063,-1.6847103589 H,1.9145978993,-2.2166721637,-0.7691674799 H,4.2673673985,-2.7465850528,0.1216269308 H,2.4537673461,-1.2423906833,2.0785520928 H,5.6212148151,-0.6770589515,0.0388617764 H,4.0262644364,0.8114023173,-1.2049878791 H,4.6986843517,-2.257759165,1.7569953354 N,0.3502506511,-1.5098390098,0.3901774465 H,0.2098443146,-0.9235117773,1.2122652541 N,1.4028094301,0.2160500962,-1.6035207162 H,1.7380616616,1.0874316268,-2.0081336677 C,-0.0230949069,0.3543159839,-1.2623554441 H,-0.5408152146,0.5164383202,-2.216093209 C,-0.4768421851,-1.0192000603,-0.7162589363 H,-0.2797861154,-1.7107315345,-1.5484544184 C,-0.3036787236,1.5794518557,-0.3846324262 C,-0.6767389005,3.9443525192,1.1031283012 C,-0.8336287721,1.5395498151,0.9080157768 C,0.0182604272,2.833965984,-0.9193472963 C,-0.1638013655,4.0037507971,-0.1912279133 C,-1.0143888229,2.7098112474,1.6454479298 H,-1.1481211161,0.5988497531,1.3469653926 H,0.408873273,2.8960716105,-1.9335700695 H,0.0891598471,4.9618336771,-0.6348771961 H,-1.4281116319,2.6499356058,2.647362972 H,-0.8208402137,4.8536521212,1.6779301109 350 C,-1.9582236216,-1.1290653625,-0.3834648405 C,-4.6923549704,-1.4308343447,0.197317889 C,-2.3939867989,-2.0946252889,0.5294923507 C,-2.9152744229,-0.3168555272,-1.0005601667 C,-4.2692215465,-0.4672353988,-0.7141121261 C,-3.7481786871,-2.2436331263,0.8178931594 H,-1.6556503247,-2.727173465,1.0102274711 H,-2.6106372916,0.4521230262,-1.703694946 H,-4.9943877268,0.1770942289,-1.2016241897 H,-4.0647976419,-2.9995872432,1.5302435335 H,-5.7480266285,-1.5450285801,0.4226481709 2cbenzene (Diamine product 2c in benzene) trans-diax-diph-tetrahydroquinoxaline_benzene M062X/6-31G(d,p) E(RM062X) = -885.7572334 Zero-point correction= 0.407381 (Hartree/Particle) Thermal correction to Energy= 0.425023 Thermal correction to Enthalpy= 0.425968 Thermal correction to Gibbs Free Energy= 0.361760 Sum of electronic and ZPE= -885.349852 Sum of electronic and thermal Energies= -885.332210 Sum of electronic and thermal Enthalpies= -885.331266 Sum of electronic and thermal Free Energies= -885.395473 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 266.706 73.334 135.136 H,2.1144856235,1.2421600689,-2.5677248057 C,2.1918560251,1.2872764176,-1.4745947378 C,2.6701718611,2.7794694353,0.5054826218 C,0.9396751419,0.9598701892,0.6738101853 C,1.3371175049,2.3604555832,1.1296500674 C,0.8562749922,0.8965179983,-0.8493579524 C,2.6174027375,2.6860448016,-1.0223243226 H,3.4659102972,2.1213514604,0.8787169202 H,1.7269340767,0.2467991727,0.9843985133 H,0.5438249267,3.0591427199,0.832912578 H,0.08810415,1.629319468,-1.1618120739 H,1.8976904694,3.4227474085,-1.4029899099 H,2.9446403614,0.546717839,-1.1738977112 H,2.9285409177,3.797016524,0.8157454955 H,1.3979763592,2.3885047311,2.2243940806 H,3.5908306838,2.941747656,-1.4529909937 351 N,0.4995411516,-0.4684931667,-1.2266489276 H,0.4667419014,-0.5393348857,-2.2422552299 N,-0.3694322078,0.6029805901,1.2139312411 H,-0.3431325431,0.6671039968,2.2301728548 C,-0.8135955235,-0.7526550983,0.8449011979 H,-1.8625097963,-0.8268976011,1.15708601 C,-0.7977346848,-0.9129002582,-0.6873993707 H,-0.8615969326,-1.9888818899,-0.8908142162 C,-0.0543390622,-1.8439260556,1.5939834812 C,1.3041398869,-3.76562785,3.1288891348 C,1.0810373003,-2.486201652,1.0877522441 C,-0.4959351396,-2.1832847766,2.8776319987 C,0.1742933125,-3.1330489728,3.6423006563 C,1.7517013338,-3.4400674662,1.8515568646 H,1.4356465973,-2.2254840258,0.0952320464 H,-1.3848035402,-1.6992967324,3.2779438957 H,-0.189574236,-3.385333156,4.6336944295 H,2.6305911006,-3.9307118355,1.4440169181 H,1.8293097997,-4.5098815745,3.7194102976 C,-1.9823619907,-0.2613149004,-1.3949031595 C,-4.0895680389,0.8864633221,-2.856623389 C,-2.6163225293,0.8992503717,-0.9376835445 C,-2.424164193,-0.8350829419,-2.5922026217 C,-3.4661374012,-0.2695736095,-3.3205345451 C,-3.6623113231,1.4651608422,-1.664801498 H,-2.2768808888,1.3559401712,-0.0130043695 H,-1.9469644884,-1.7445933266,-2.9522753606 H,-3.7967355165,-0.7351255347,-4.2440467574 H,-4.1450786005,2.3652581781,-1.2959811229 H,-4.9052599026,1.3304183314,-3.4187470594 The below coordinates use the 6-31+G(d,p) basis set in acetonitrile. HF hf_mecn_6-31+gdp M062X/6-31+G(d,p) E(RM062X) = -100.4203466 Zero-point correction= 0.009207 (Hartree/Particle) Thermal correction to Energy= 0.011568 Thermal correction to Enthalpy= 0.012512 Thermal correction to Gibbs Free Energy= -0.007218 Sum of electronic and ZPE= -100.411139 Sum of electronic and thermal Energies= -100.408779 Sum of electronic and thermal Enthalpies= -100.407835 Sum of electronic and thermal Free Energies= -100.427564 352 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 7.259 4.968 41.525 F,-1.4028831714,-0.57422968,0. H,-2.3342596686,-0.57422968,0. B2F4 mecn_b2f4_flat M062X/6-31+G(d,p) E(RM062X) = -449.1826894 Zero-point correction= 0.018903 (Hartree/Particle) Thermal correction to Energy= 0.024889 Thermal correction to Enthalpy= 0.025833 Thermal correction to Gibbs Free Energy= -0.010879 Sum of electronic and ZPE= -449.163786 Sum of electronic and thermal Energies= -449.157801 Sum of electronic and thermal Enthalpies= -449.156856 Sum of electronic and thermal Free Energies= -449.193568 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 15.618 18.194 77.266 B,0.,0.,0.8586809469 B,0.,0.,-0.8586809469 F,-0.0396044168,1.127336663,-1.5581135504 F,0.0396044168,-1.127336663,-1.5581135504 F,0.0396044168,1.127336663,1.5581135504 F,-0.0396044168,-1.127336663,1.5581135504 E,E-(18) (E,E-18 in acetonitrile, see Scheme 4.5) mecn_edadiim_EE M062X/6-31+G(d,p) E(RM062X) = -728.5611576 Zero-point correction= 0.284209 (Hartree/Particle) Thermal correction to Energy= 0.299812 Thermal correction to Enthalpy= 0.300756 Thermal correction to Gibbs Free Energy= 0.237562 Sum of electronic and ZPE= -728.276949 Sum of electronic and thermal Energies= -728.261346 Sum of electronic and thermal Enthalpies= -728.260401 Sum of electronic and thermal Free Energies= -728.323596 353 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 188.135 59.755 133.004 C,2.3602461042,-0.6947194916,-0.3278372236 C,2.3602130668,0.6948547879,0.327892545 H,2.3326740211,-0.5782077885,-1.4207964714 H,2.3326286093,0.5783409941,1.420851139 N,1.2319851704,1.4612304756,-0.1703037103 N,1.2320423669,-1.4611404594,0.1703425255 C,0.2220826733,1.5748736279,0.5948593377 H,0.2228924075,1.1603675941,1.6138651661 C,0.2221675647,-1.5748554792,-0.594846171 H,0.2229832548,-1.1603747872,-1.6138625003 C,-1.0256233586,-2.2507767953,-0.1829938424 C,-1.1684824128,-2.8324166004,1.0848089898 C,-2.0941014775,-2.2953830134,-1.0851649239 C,-2.3635263293,-3.450740225,1.4375468959 H,-0.3381777353,-2.7949243085,1.7836578056 C,-3.2929873166,-2.9138049961,-0.7298725191 H,-1.9817085356,-1.8414697584,-2.0669828318 C,-3.4285593721,-3.4920874271,0.5316401954 H,-2.4698227117,-3.9012153154,2.4199195523 H,-4.1177293285,-2.9431843808,-1.4354820961 H,-4.3602643716,-3.9748548159,0.8114253327 C,-1.0257337841,2.250735477,0.1829874731 C,-2.0942520493,2.2952282902,1.0851166771 C,-1.1685787047,2.8324239279,-1.0847943283 C,-3.2931655369,2.9135836822,0.729801754 H,-1.9818688283,1.841279368,2.0669193077 C,-2.363649302,3.4506839223,-1.437553255 H,-0.338243136,2.7950165881,-1.7836110698 C,-3.4287239097,3.4919145177,-0.5316901339 H,-4.1179404374,2.9428720343,1.43537674 H,-2.4699359139,3.9011968479,-2.4199096864 H,-4.3604505042,3.9746300623,-0.8114928093 H,3.2862229236,1.2057405656,0.0478226238 H,3.2862722935,-1.2055675707,-0.0477520279 A (Ionic complex A, see Scheme 4.5) mecn_b2f4_edadiim-EE_sm M062X/6-31+G(d,p) E(RM062X) = -1177.8007951 Zero-point correction= 0.308786 (Hartree/Particle) 354 Thermal correction to Energy= 0.329557 Thermal correction to Enthalpy= 0.330501 Thermal correction to Gibbs Free Energy= 0.257878 Sum of electronic and ZPE= -1177.492009 Sum of electronic and thermal Energies= -1177.471238 Sum of electronic and thermal Enthalpies= -1177.470294 Sum of electronic and thermal Free Energies= -1177.542917 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 206.800 80.909 152.848 C,-0.7134777051,2.1050772493,0.0852494819 C,0.6929597717,2.0179705924,-0.5240353021 H,-0.675507583,2.5573898217,1.077378439 H,0.6244369273,1.9568070301,-1.611437378 N,1.4314684289,0.8352203584,-0.033462663 N,-1.3273543468,0.7779970981,0.2516764183 C,2.1655059864,0.2125159768,-0.8822215924 H,2.2576289347,0.6584989022,-1.8752397266 C,-2.2193044765,0.4128658679,-0.5986352343 H,-2.4035674764,1.0766305296,-1.4469738905 B,1.0593606955,0.5091564003,1.522224835 B,-0.5916750351,-0.0627356207,1.472204641 F,1.2541329191,1.7734398951,2.1645132938 F,2.0287810545,-0.367135168,2.0509465676 F,-1.3768308068,0.1897523729,2.6303652088 F,-0.6929334166,-1.4379830972,1.1428720548 C,-3.048255564,-0.7928767532,-0.5460021485 C,-3.4436012499,-1.3895121794,0.6601148902 C,-3.5275069187,-1.2946694957,-1.7646000737 C,-4.2821956,-2.4985792489,0.6370672801 H,-3.1096697058,-0.9727685811,1.6040324916 C,-4.3466374749,-2.4200060121,-1.7828580073 H,-3.2474248507,-0.8044278192,-2.6933019874 C,-4.723317388,-3.0215562963,-0.5813656655 H,-4.5968778605,-2.9548476822,1.5703129247 H,-4.7015811772,-2.8171968339,-2.7284368836 H,-5.3744044564,-3.8906050595,-0.5920325653 C,2.899761382,-1.0480139009,-0.6969315103 C,4.1412773498,-1.1608387428,-1.3378548793 C,2.3590357614,-2.1505852269,-0.0222494852 C,4.8694999193,-2.3440822084,-1.2472089328 H,4.5362377322,-0.3158661738,-1.8959618352 C,3.0784800466,-3.3403347511,0.0390675729 H,1.3773186971,-2.0777789861,0.4335051328 355 C,4.337418792,-3.4347415299,-0.5583510298 H,5.8407856883,-2.419734746,-1.7257637199 H,2.6547598711,-4.1973113946,0.5534225731 H,4.8962048181,-4.364010074,-0.4996431833 H,1.2482399787,2.9178629173,-0.247491777 H,-1.3336806922,2.7297914398,-0.5596976642 B (Ionic complex B, see Scheme 4.5) zwit-hf_b2f4_edadiim_EE_sm_6-31+gdp-acn M062X/6-31+G(d,p) E(RM062X) = -1278.2523465 Zero-point correction= 0.323435 (Hartree/Particle) Thermal correction to Energy= 0.346308 Thermal correction to Enthalpy= 0.347252 Thermal correction to Gibbs Free Energy= 0.268776 Sum of electronic and ZPE= -1277.928911 Sum of electronic and thermal Energies= -1277.906039 Sum of electronic and thermal Enthalpies= -1277.905095 Sum of electronic and thermal Free Energies= -1277.983571 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 217.311 87.029 165.167 C,1.5880335878,-2.1239896278,-0.3525611285 C,1.8979727059,-1.0189927093,0.6739453646 H,1.8200287512,-1.7871454253,-1.3624814317 H,1.7133182494,-1.380579223,1.6878419145 N,1.0570391603,0.1540104832,0.3998047937 N,0.1648783886,-2.4570825405,-0.2950731996 C,-0.0151732951,0.2596861514,1.1100128069 H,-0.1490806008,-0.4956527383,1.8877607315 C,-0.7268836385,-1.818162076,-0.9767690671 H,-0.3486773456,-1.1045126155,-1.7108181699 B,1.5655609998,1.1448048461,-0.8104053076 B,2.1164568239,2.6872359324,-0.1752664791 F,0.4728420722,1.1503241855,-1.7378174553 F,2.6081125745,0.4014914195,-1.4447146606 F,1.5819763981,3.8180306741,-0.8969694061 F,3.5472358285,2.8188836194,-0.2454039535 C,-2.1614653593,-1.9106168269,-0.8015896708 C,-2.7829466435,-2.8232980942,0.0691864193 C,-2.9267639027,-0.9560180984,-1.4908914221 C,-4.1580218365,-2.767904287,0.2446856045 H,-2.2067998963,-3.575911757,0.6001881562 356 C,-4.3040944109,-0.901983466,-1.3017733178 H,-2.4317361293,-0.2533165479,-2.1560577794 C,-4.9160170243,-1.8058740048,-0.4339914115 H,-4.6452556579,-3.4710620122,0.9120152072 H,-4.8949031573,-0.1575446708,-1.8250978854 H,-5.9905296431,-1.7660574168,-0.2828178019 C,-1.1425105209,1.1901014542,1.0137352187 C,-2.278132074,0.7929019215,1.7442767466 C,-1.1935994291,2.3776709473,0.264169211 C,-3.4498133466,1.5419503789,1.7051022447 H,-2.2402194029,-0.1169418194,2.3385207288 C,-2.3617885115,3.1320193106,0.2448445195 H,-0.3355245165,2.7211830038,-0.2955849925 C,-3.4923588843,2.7145507441,0.9519055353 H,-4.3212422218,1.214017543,2.2628881672 H,-2.3911005153,4.0515245877,-0.3313273773 H,-4.4015249701,3.3074954775,0.919161116 H,-0.1235521842,-3.1099927548,0.4351292056 F,1.7733251178,2.9081912002,1.2083768142 H,2.9479648345,-0.7448367385,0.572418734 H,2.1626226257,-3.0189554297,-0.1137273222 C (Ionic transition state C, see Scheme 4.5) zwit-hf_loaded-geom_b2f4_edadiim_EE_ts-guess M062X/6-31+G(d,p) E(RM062X) = -1278.2154898 Zero-point correction= 0.321524 (Hartree/Particle) Thermal correction to Energy= 0.343857 Thermal correction to Enthalpy= 0.344801 Thermal correction to Gibbs Free Energy= 0.269103 Sum of electronic and ZPE= -1277.893966 Sum of electronic and thermal Energies= -1277.871633 Sum of electronic and thermal Enthalpies= -1277.870688 Sum of electronic and thermal Free Energies= -1277.946386 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 215.774 85.803 159.320 C,1.5106163922,-1.8201385667,-1.0917909247 C,1.8824524733,-0.9881702541,0.1494670387 H,1.6357344226,-1.2218331555,-1.9981784269 H,1.6752747009,-1.559790782,1.0584386095 N,1.1079209401,0.2616892811,0.1735209131 N,0.1296209672,-2.2531618249,-0.9950048473 357 C,-0.1744102903,0.1210014382,0.5898360472 H,-0.3327282105,-0.6560037533,1.3366283351 C,-0.8320697585,-1.3531952244,-1.1009065123 H,-0.643955096,-0.529235557,-1.7872232222 B,1.8767103478,1.4952889236,-0.0794988852 B,2.3651591438,1.5524615704,1.8611361673 F,1.2290487499,2.6902953972,-0.2860268917 F,3.0036472171,1.3507221295,-0.8705094441 F,1.1919107315,1.7305388128,2.5697012155 F,3.153984657,2.6971604229,1.8474110344 C,-2.2158603269,-1.6090413578,-0.7093144312 C,-2.5487360629,-2.5036774133,0.3195886163 C,-3.2252854597,-0.8778086212,-1.3521173775 C,-3.8801374562,-2.6740863881,0.6830604388 H,-1.7738111501,-3.0445287666,0.8570471053 C,-4.5564811877,-1.0536927152,-0.984843345 H,-2.9589278746,-0.1764331422,-2.1381057558 C,-4.8840355598,-1.9514070528,0.0319803549 H,-4.1360639029,-3.3613985483,1.4830523301 H,-5.3349464482,-0.4876801892,-1.4866725519 H,-5.9211983643,-2.0835713159,0.3249105581 C,-1.2264070542,1.1221757131,0.4592995854 C,-2.2316086008,1.1488988727,1.4439734122 C,-1.3764645596,1.9432404085,-0.6729127596 C,-3.3296480077,1.9949213467,1.3209902011 H,-2.1407035009,0.497503964,2.3102166604 C,-2.4724792786,2.7950302829,-0.7881493094 H,-0.6467696559,1.8965928509,-1.47537091 C,-3.4514391998,2.8290980794,0.2068072338 H,-4.0915903356,2.0038135024,2.0950671081 H,-2.5705263225,3.4232416382,-1.6688337845 H,-4.307405032,3.4900161898,0.1092652801 H,-0.0434109897,-3.0963657599,-0.452670585 F,3.079665726,0.4427967086,2.2774949255 H,2.9445566961,-0.7586247981,0.1051566909 H,2.1564491004,-2.6967190764,-1.1422405576 D (Sigmatropic transition state D, see Scheme 4.5) acetonitrile_6-31+gdp_m062x_b2f4_edadiim_EE_ts-guess_hf M062X/6-31+G(d,p) E(RM062X) = -1177.7767617 Zero-point correction= 0.309168 (Hartree/Particle) Thermal correction to Energy= 0.328889 Thermal correction to Enthalpy= 0.329833 Thermal correction to Gibbs Free Energy= 0.261517 358 Sum of electronic and ZPE= -1177.467594 Sum of electronic and thermal Energies= -1177.447873 Sum of electronic and thermal Enthalpies= -1177.446929 Sum of electronic and thermal Free Energies= -1177.515245 E CV S KCal/Mol Cal/Mol-K Cal/Mol-K Total 206.381 78.536 143.784 C,2.3538222227,0.808006789,-0.2830796865 C,2.2932282981,-0.6940355582,-0.727625425 H,3.0991072977,0.9415089615,0.4991993797 H,2.1989723998,-0.7763178267,-1.80941343 N,1.1086454307,-1.3143588086,-0.1065475626 N,1.0410397326,1.1993409758,0.2555111408 C,0.0211369625,-1.240413083,-0.8716977484 H,0.2263906162,-1.1114773306,-1.9306514039 C,0.0885442649,1.2495727916,-0.6750793973 H,0.4287719391,1.1873527378,-1.7066256354 B,1.2155079934,-1.304198987,1.3754072045 B,0.8976458959,0.7322124219,1.6749380455 F,2.5029261773,-1.5141884521,1.8429399723 F,0.2826372463,-2.0032916625,2.104498846 F,1.9265211919,1.12380421,2.5111455927 F,-0.3317335332,0.8120796086,2.2861328185 C,-1.290016823,1.6940029604,-0.4791031257 C,-1.7070868381,2.4889534995,0.599589412 C,-2.2270326901,1.3455546909,-1.4690248729 C,-3.0417104365,2.8754861825,0.7092482856 H,-0.9868059081,2.8250249194,1.336672304 C,-3.557668528,1.7286322741,-1.3540338368 H,-1.9022630885,0.7532500939,-2.3210602201 C,-3.9721590695,2.4861266079,-0.2548273939 H,-3.3528171128,3.4917878654,1.5473676114 H,-4.2716470098,1.4374097154,-2.1186799283 H,-5.0114604488,2.786392654,-0.1609462006 C,-1.3649891716,-1.6132764531,-0.5647062108 C,-2.0972646999,-2.1636810397,-1.6311684443 C,-2.0364057874,-1.3211949241,0.6335036559 C,-3.4501049922,-2.4603881149,-1.4923311035 H,-1.5954496256,-2.3567402805,-2.576188715 C,-3.3927837076,-1.6073784146,0.7643215298 H,-1.5140954238,-0.8432431516,1.4510725082 C,-4.1030549677,-2.1835096382,-0.2905506994 H,-3.9947004255,-2.8965301015,-2.3242063208 H,-3.8998333225,-1.3661221833,1.6938689483 359 H,-5.1608513079,-2.4029296467,-0.1803659389 H,3.1916402235,-1.2143014802,-0.4000992243 H,2.5995858353,1.4450075374,-1.1334009107 360 REFERENCES 361 REFERENCES (1) Carter, C. A. G.; John, K. D.; Mann, G.; Martin, R. L.; Cameron, T. M.; Baker, R. T.; Bishop, K. L.; Broene, R. D.; Wescott, S. A. Bifunctional Lewis Acid Reactivity of Diol-Derived Diboron Reagents. ACS Symposium Series: Group 13 Chemistry 2002, 822, 70–87. (2) Chen, D.; Xu, G.; Zhou, Q.; Chung, L. W.; Tang, W. Practical and Asymmetric Reductive Coupling of Isoquinolines Templated by Chiral Diborons. J. Am. Chem. Soc. 2017, 139, 9767–9770. (3) Zhou, M.; Li, K.; Chen, D.; Xu, R.; Xu, G.; Tang, W. Enantioselective Reductive Coupling of Imines Templated by Chiral Diboron. J. Am. Chem. Soc. 2020, 142, 10337–10342. (4) Zhang, L.; Jiao, L. Super electron donors derived from diboron. Chem. Sci. 2018, 9, 2711–2722. (5) Alam, R.; Das, A.; Huang, G.; Eriksson, L.; Himo, F.; Szabó, K. J. Stereoselective allylboration of imines and indoles under mild conditions. An in situ E/Z isomerization of imines by allylboroxines. Chem. Sci. 2014, 5, 2732–2738. (6) Cade, I. A. Chau, W. Y.; Vitorica-Yrezabal, I.; Ingleson, M. J. 1,1/1,2 Isomerisation in Lewis base adducts of B2cat2. Dalton Trans. 2015, 44, 7506–7511. (7) Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016. (8) Zhao, Y.; Schultz, N. E.; Truhlar, D. G. Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions J. Chem. Theory. Comput. 2006, 2, 364–382. 362 (9) Zhao, Y.; Truhlar, D. G. A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J. Chem. Phys. 2006, 125, 194101–194118. (10) Zhao, Y.; Truhlar, D. G. Density Functional for Spectroscopy: No Long-Range Self- Interaction Error, Good Performance for Rydberg and Charge-Transfer States, and Better Performance on Average than B3LYP for Ground States. J. Phys. Chem. A 2006, 110, 13126–13130. (11) Lawlor, F. J.; Norman, N. C.; Pickett, N. L.; Robins, E. G.; Nguyen, P.; Lesley, G.; Marder, T. B.; Ashmore, J. A.; Green, J. C. Bis-Catecholate, Bis-Dithiocatecholate, and Tetraalkoxy Diborane(4) Compounds: Aspects of Synthesis and Electronic Structure. Inorg. Chem. 1998, 37, 5282–5288. 363 Chapter 5. An Improved Preparation of Tetraalkoxydiborons and Diboron Diolates from Tetrahydroxydiboron Introduction. As detailed in previous chapters, diboron diolates (and other diborons) have broad applications in many reactions,1-5 and while they are generally bench stable compounds, their preparation can be tedious. Boron-boron bonds are commercially prepared via the Wurtz coupling of halobis(dialkylamino)boranes (Scheme 5.1a).6-7 While tetrakis(dialkylamino)diborons of this type do have applications in synthesis,8-10 diboron diolates are far more widely used.1-5 Their direct preparation from tetracids(dialkylamino)diborons requires the use of a dry solution of HCl in Et2O at -78 °C, followed by tedious filtration of dialkylammonium hydrochloride salts, then distillation, sublimination, or crystallization of the diboron diolate (Scheme 5.1b).6-7 However, B2(OH)4 is also readily prepared via hydrolysis of tetrakis(dialkylamino)diboron.11 Diboron diolates can be synthesized by stirring a heterogeneous mixture of B2(OH)4 with a diol and MgSO4 for 24 hours (Scheme 5.1c).12 364 Scheme 5.1. Previously reported syntheses of diboron diolates and similar compounds. Inspired by a previous report for the preparation of PhB(OMe)2 from PhB(OH)2 by reaction with trimethyl orthoformate in the presence of an acid catalyst (Scheme 5.1d),13 we have developed an exceptionally fast and convenient method for the preparation of diboron diolates and tetraalkoxydiborons (Scheme 5.2). The use of this method is much easier and more practical than the previously reported methods. 365 Scheme 5.2. This work. 366 Scope of the Reaction. The AcCl-catalyzed reaction of B2(OH)4 (30) with CH(OMe)3 is complete within minutes at room temperature, is not particularly air sensitive, and offers a visual indicator of completion, producing a homogenous solution [containing B2(OMe)4 (31), MeOH, and methyl formate] after consumption of starting material. The diol is then added, the solution stirred briefly, and the solvent removed in vacuo to afford the desired diboron in high yield, typically without a need for further purification (Scheme 2, bottom). A variety of diboron diolates (compounds 32-39) were prepared on gram scale (Table 5.1) using this methodology. Reactions with aliphatic 1,2-diols (Entries 1-3), aliphatic 1,3-diols (Entries 4-6) and phenols such as catechol or 2-hydroxybenzyl alcohol (Entries 7-8) were successful. Conversion was low with diisopropyl tartrate, and perfluoropinacol failed to afford any product, likely due to diminished nucleophilicity relative to the other substrates. Attempts to separate B2(OMe)4 (31) from the MeOH byproduct by distillation were unsuccessful. Interestingly, the anhydride of B2(OH)4 can be prepared quantitatively by heating under vacuum for several hours, generating (B2O2)n (40) as a hard white solid.11,14 This material failed to react with CH(OMe)3 in the presence of catalytic AcCl, but did so with dry HCl in Et2O (Scheme 5.2, top). These reactions are much slower than those with B2(OH)4 (48 hours instead of 5 minutes) and require gentle heating (40 °C instead of room temperature). Removal of residual (B2O2)n (40) by filtration, and Et2O and methyl formate by distillation (which is trivial, given the wide separation in boiling points vs. B2(OMe)4) (31), afforded B2(OMe)4 (31) (Scheme 5.3) in high yield, containing a small amount of residual B(OMe)3. 367 Table 5.1. Scope of the reaction: diboron diolates (32-39) prepared from 30. Entry (diboron) Diol Yield (%)a 1 (32) Ethylene glycol 92 2 (33) Propylene glycol 99 3 (34) (1S,2S)-1,2-Diphenylethylene glycol 97 4 (35) 1,3-Butanediol 99 5 (36)b Neopentyl glycol 95 6 (37) Hexylene glycol 94 7 (38) Catechol 98 8 (39)b 2-Hydroxybenzyl alcohol 97 a Isolated yield. b Dichloromethane was added after addition of the diol to improve the homogeneity of the reaction mixture. We also attempted to prepare B2(OEt)4 (41) via this method, and obtained a mixture whose primary spectral features were consistent with its structure. However, our assignment is not secure due to the complexity of the spectra. (Caution: unlike B2(OMe)4, the reaction of B2(OEt)4 with air is spontaneous and is very exothermic!) This is a simple alternative to previous methods for their synthesis from tetrakis(dialkylamino)diborons.6 Scheme 5.3. Synthesis of tetramethoxydiboron (31). 368 Conclusions. To summarize, we have developed a simple, convenient, and high yielding method for the preparation of both diboron diolates and tetraalkoxydiborons using bench stable B2(OH)4 as a universal precursor. Diboron diolates were prepared via pre-treatment with acetyl chloride and trimethyl orthoformate, followed by addition of the diol. This method was largely substrate tolerant with respect to the diol. Tetraalkoxydiborons were prepared by thermal/vacuum dehydration of B2(OH)4 to yield (B2O2)n, followed by treatment with a trialkyl orthoformate in the presence of acid. Experimental Section. General. All reactions were carried out under a nitrogen atmosphere in flame-dried glassware unless otherwise noted. All reagents were obtained from commercial sources and were used as obtained unless otherwise noted. Dichloromethane was obtained from commercial sources and used without further purification. Boron monoxide was prepared as previously described in the literature.11,14 Yields refer to isolated yields of compounds estimated to be ≥95% pure as determined by 1H NMR analysis unless otherwise noted. The yields reported here are the results of a single experiment. General Procedure: Preparation and Characterization of Diboron Diolates. A flask was charged with B2(OH)4 (30, 1.0 equiv) and CH(OMe)3 (4.0 equiv), and a stir bar. AcCl was added (0.0025–0.01 equiv), the vessel flushed with N2 and sealed with a silicone septum, and the mixture stirred rapidly at room temperature until all solid material had dissolved (5 minutes or less, determined by stir rate and the grain size of the B2(OH)4). 369 The diol was then added and stirred for 30 minutes. Solvent was removed in vacuo via rotary evaporation to afford the title compound. 32 2,2′-Bi(1,3,2-dioxaborolane) (32). The title compound was prepared from B2(OH)4 (30, 2.24 g, 25 mmol), CH(OMe)3 (10.94 mL, 100 mmol), 1 mol % AcCl (18 µL, 0.25 mmol), and ethylene glycol (2.8 mL, 50 mmol) according to the general procedure. The solid material was then washed twice with cold dichloromethane. This procedure afforded 3.24 g (92%) of the title compound as a white solid: mp = 133–149 °C (lit. mp12 = 159-160 °C, lit. mp22 = 168-170 °C). 1H, 13C, and 11B NMR data12 were consistent with literature values: 1H NMR (500 MHz, CDCl3) δ 4.21 (s, 8H); 13C{1H} NMR (126 MHz, CDCl3) δ 65.5; 11B NMR (160 MHz, CDCl3) δ 30.8. 33 4,4′-Dimethyl-2,2′-bi(1,3,2-dioxaborolane) (33). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 1 mol % AcCl (7.1 µL, 0.1 mmol), and propylene glycol (1.47 mL, 20 mmol) according to the general procedure. This procedure afforded 1.7 g (99%) of the title compound as a colorless oil: 1H NMR (500 MHz, CDCl3) δ 4.59–4.50 (m, 2H), 4.27 (dd, J = 9.0, 8.0 Hz, 2H), 3.70 (dd, J = 9.0, 7.5 Hz, 2H), 1.31 (d, J = 6.2 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 73.5, 72.0, 21.7; 11B NMR (160 MHz, CDCl3) δ 30.8. 370 34 (4S,4S′,5S,5S′)-4,4′,5,5′-Tetraphenyl-2,2′-bi(1,3,2-dioxaborolane) (34). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 1 mol % AcCl (7.1 µL, 0.1 mmol), and (1S,2S)-1,2-diphenylethylene glycol (4.29 g, 20 mmol) according to the general procedure. This procedure afforded 4.33 g (97%) of the title compound as a very pale pink-white solid: mp = 136–140 °C. 1H and 13C NMR data15-16 were consistent with literature values: 1H NMR (500 MHz, CDCl3) δ 7.45– 7.35 (m, 20H), 5.30 (s, 4H); 13 C{1H} NMR (126 MHz, CDCl3) δ 139.8, 128.8, 128.4, 126.0, 86.7; 11B NMR (160 MHz, CDCl3) δ 31.9. 35 4,4′-Dimethyl-2,2′-bi(1,3,2-dioxaborinane) (35). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 1 mol % AcCl (7.1 µL, 0.1 mmol), and 1,3-butanediol (1.79 mL, 20 mmol) according to the general procedure. This procedure afforded 1.98 g (99%) of the title compound as a colorless viscous oil. 1H NMR data17 were consistent with reported values. 1H NMR (500 MHz, CDCl3) δ 4.14–4.06 (m, 2H), 3.98–4.03 (m, 2H), 3.89–3.96 (m, 2H), 1.88–1.95 (m, 2H), 1.74–1.65 (m, 2H), 1.27 (d, J = 6.3 Hz, 6H); 13 C{1H} NMR (126 MHz, CDCl3) δ 66.7, 60.5, 34.2, 22.8; 11B NMR (160 MHz, CDCl3) δ 28.3. 371 36 5,5,5′,5′-Tetramethyl-2,2′-bi(1,3,2-dioxaborinane) (36). The title compound was prepared from B2(OH)4 (30, 2.24 g, 25 mmol), CH(OMe)3 (10.94 mL, 100 mmol), 0.25 mol % AcCl (4.4 µL, 0.0625 mmol), and neopentyl glycol (5.21 g, 50 mmol) according to the general procedure. Dichloromethane (5 mL) was added after addition of the neopentyl glycol to improve the homogeneity of the reaction mixture. This procedure afforded 5.35 g (95%) of the title compound as a white solid: mp = 128–147 °C (lit. mp20 = 182.5–184.5 °C). 1H and 13C NMR data18, and 11B NMR data19 were consistent with reported values. 1H NMR (500 MHz, CDCl3) δ 3.55 (s, 8H), 0.91 (s, 12H); 13C{1H} NMR (126 MHz, CDCl3) δ 71.5, 31.6, 22.1; 11B NMR (160 MHz, CDCl3) δ 27.8. 37 4,4,4′,4′,6,6′-Hexamethyl-2,2′-bi(1,3,2-dioxaborinane) (37). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 1 mol % AcCl (7.1 µL, 0.1 mmol), and hexylene glycol (2.57 mL, 20 mmol) according to the general procedure. This procedure afforded 2.38 g (94%) of the title compound as a white solid: mp = 96–99 °C (lit. mp20 = 99–101.6 °C). 1H and 13C NMR data18 were consistent with reported values: 1H NMR (500 MHz, CDCl3) δ 4.17–4.08 (m, 2H), 1.73–1.68 (m, 2H), 13 1.44–1.52 (m, 2H), 1.27–1.24 (m, 12H), 1.24–1.21 (m, 6H); C{1H} NMR (126 MHz, CDCl3) δ 70.0, 64.0, 46.2, 31.2, 28.4, 23.2; 11B NMR (160 MHz, CDCl3) δ 28.1. 372 38 2,2′-Bibenzo[d][1,3,2]dioxaborole (38). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 0.5 mol % AcCl (3.6 µL, 0.05 mmol), and catechol (2.20 g, 20 mmol) according to general procedure. This procedure afforded 2.34 g (98%) of the title compound as an off-white solid, consisting of 5% catechol by mass: mp = 172–176 °C (lit. mp22 = 195–198°C). 1H data and 11B data21 were consistent with reported values: 1H NMR (500 MHz, CDCl3) δ 7.39 (dd, J = 5.9, 3.3 Hz, 4H), 7.19 (dd, J = 5.9, 3.3 Hz, 4H); 13C{1H} NMR (126 MHz, CDCl3) δ 147.7, 123.4, 113.1; 11B NMR (160 MHz, CDCl3) δ 31.0. 39 4H,4H′-2,2′-Bibenzo[d][1,3,2]dioxaborinine (39). The title compound was prepared from B2(OH)4 (30, 0.90 g, 10 mmol), CH(OMe)3 (4.38 mL, 40 mmol), 0.5 mol % AcCl (3.6 µL, 0.05 mmol), and 2-hydroxybenzyl alcohol (2.48 g, 20 mmol) according to general procedure. Dichloromethane (10 mL) was added after addition of the 2- hydroxybenzyl alcohol to improve the homogeneity of the reaction mixture. This procedure afforded 2.57 g (97%) of the title compound as an orange solid: mp = 110–126 °C. 1H NMR data17 were consistent with reported values: 1H NMR (500 MHz, CDCl3) δ 7.23– 13 7.18 (m, 2H), 7.01–7.09 (m, 4H), 6.91–6.95 (m, 2H), 5.12 (s, 4H); C{1H} NMR (126 373 MHz, CDCl3) δ 147.8, 128.7, 124.8, 123.5, 122.7, 118.0, 61.9; 11 B NMR (160 MHz, CDCl3) δ 27.9. 31 Tetramethoxydiboron (31). A 1-dram vial was charged with a stir bar, B2O2 (40, 268 mg, 5 mmol), CH(OMe)3 (1.15 mL, 10.5 mmol), and 2 M HCl in Et2O (0.25 mL, 0.5 mmol). The vial was flushed with N2 and capped, then stirred at 40 °C for 48 h. The cap was replaced with a septum, and connected to a water aspirator by a length of PTFE tubing. HCO2Me and Et2O were removed via vacuum distillation (400 mmHg) at room temperature, gradually raising the temperature over an hour to 40 °C. The remaining liquid was then filtered through glass wool under a N2 atmosphere. This procedure afforded 608 mg of the title compound in 91% purity (containing 4% methyl formate, 2% methanol, 3% diethyl ether) as a colorless oil, for an overall yield of 553 mg (76%). B(OMe)3 content 11 was judged by B NMR to be <1%. The relative proportions of each component were estimated via spectral deconvolution using the line fitting protocol in MNova 14.2.0 (Mestrelab Research, S.L.; Santiago de Compostela, Spain) using Gaussian/Lorentzian peak shapes and simulated annealing. 1 H NMR (500 MHz, CDCl3) δ 3.61 (s, 12H); 13 C{1H} NMR (126 MHz, CDCl3) δ 51.9; 11B NMR (160 MHz, CDCl3) δ 31.2. 374 41 Tetraethoxydiboron (41). A 1-dram vial was charged with a stir bar, B2O2 (40, 268 mg, 5 mmol), CH(OEt)3 (1.75 mL, 10.5 mmol), and 2 M HCl in Et2O (0.25 mL, 0.5 mmol). The vial was flushed with N2 and capped, then stirred at 40 °C for 48 h. The cap was replaced with a septum, and connected to a water aspirator by a length of PTFE tubing. Et2O was removed via vacuum distillation (400 mmHg) at room temperature, and the temperature was then gradually raised over an hour to 40 °C to remove HCO2Et. The remaining liquid was then filtered through glass wool under a N2 atmosphere. This procedure afforded 810 mg of an impure colorless oil. Its spectral features were consistent with B2(OEt)4 being the primary component, although our assignment is not secure, and we were unable to easily assess its purity based on spectral data due to the complexity of its spectra. 1H NMR (500 MHz, CDCl3) δ 4.23–3.97 (m, 4H), 3.93 (q, J = 7.1 Hz, 4H), 1.25 (t, J = 7.1 Hz, 6H), 1.20 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (126 MHz, CDCl3) δ 60.0, 17.6; 11B NMR (160 MHz, CDCl3) δ 31.0. 375 APPENDIX 376 Spectral Data. 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 406 REFERENCES 407 REFERENCES (1) Neeve, E. C.; Geier, S. J.; Mkhalid, I. A. I.; Westcott, S. A.; Marder, T. B. 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