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mass ' LIBRARY
4 Michigan State
2009 University

——

This is to certify that the
dissertation entitled

TITANIUM-CATALYZED ADDITIONS OF SUBSTITUTED
HYDRAZTNES TO ALKYNES: CATALYST DESIGN,
MECHANISTIC STUDIES, AND APPLICATIONS IN

HETEROCYCLE SYNTHESIS

presented by

SANJUKTA BANERJEE

has been accepted towards fulfillment
of the requirements for the

Ph. D. degree in CHEMISTRY

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TITANIUM-CATALYZED ADDITIONS OF SUBSTITUTED HYDRAZINES TO
ALKYNES: CATALYST DESIGN, MECHANISTIC STUDIES, AND
APPLICATIONS IN HETEROCYCLE SYNTHESIS

VOLUME I

By

Sanj ukta Banerjee

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Chemistry

2008

ABSTRACT

TITANIUM-CATALYZED ADDITIONS OF SUBSTITUTED HYDRAZIN ES TO
ALKYNES: CATALYST DESIGN, MECHANISTIC STUDIES, AND
APPLICATIONS IN HETEROCYCLE SYNTHESIS

By

SANJUKTA BANERJEE

The primary focus of this thesis is the development of hydrohydrazination reactions
for alkynes and their applications towards the synthesis of heterocycles.
Hydrohydrazination is the formal addition of a hydrazine to an unsaturated C—C bond
resulting in hydrazone or substituted hydrazine. Hydrohydrazination reactions are closely
related to hydroamination. In hydroamination, amines (instead of hydrazines) are added
across the C—C unsaturation. While hydrohydrazination of alkyne has been developed
only recently, hydroamination has been known since 1950’s and studied extensively. To
cover sufficient background information for hydrohydrazination, hydroamination

reactions are discussed in the first chapter.

In 2002, our group first discovered the hydrohydrazination of alkynes with 1,1-
disubstituted hydrazines leading to the synthesis of N-protected indoles. Here, we have
developed a new pyrrole-based titanium catalyst that is found to be active for the
monosubstituted hydrazines. In addition, this catalyst is also active for both terminal and
internal alkynes. The design of the catalyst, substrate scope, and applications to different
heterocycles synthesis including compounds containing NH-indoles are discussed in the

second chapter.

 

Iminohydrazination is the conversion of an alkyne to an (LB-unsaturated B-
aminohydrazone, making both C—C and C—N bonds in a single step. This is a new
multicomponent reaction (MCR) between an alkyne, 1,1-disubstituted hydrazine, and
isonitn'le in the presence of a catalyst. The design of new Ti-based catalysts, the scope of
the iminohydrazination reaction, mechanistic investigation, and applications towards the

synthesis of pyrazoles are discussed in the third chapter.

Vanadium(V) hydrazido complexes have been found in the active sites of different
nitrogenase enzymes. The metal in these complexes is believed to be simultaneously
coordinated to different donating centers such as N, O, and S. To understand the
structures and fimctions of the active sites, different vanadium hydrazido complexes have
been synthesized as model compounds. Interesting structural feature involving
contributions from both hydrazido and isodiazene resonance forms has been observed in
one of the model compounds. The synthesis of different vanadium(V) hydrazido

complexes and important structural aspects are discussed in the fourth chapter.

Copyright by
Sanjukta Banetjee
2008

To my mother, Dr. Shyamali Banetjee

ACKNOWLEDGMENTS

First of all, I would like to thank Michigan State University for the support during my
years as graduate student at MSU. I also want to thank the people in the Chemistry

department for their help and generous support.

I consider myself very fortunate to have Prof. Aaron L. Odom as my Ph. D. mentor.
He was never tired of discussing science and always listened to my questions with deep
interest (even the silliest onel). He helped me a lot to learn many aspects of inorganic and
organometallic chemistry and to develop the analytical skills necessary to survive in an
experimental lab. I am also indebted to him for doing the hard work of correcting and
Proofreading this thesis. “Thank you” Aaron for your guidance, patience, and

understanding. “Sandy” has thoroughly enjoyed her experience working with you.

I eXpress my gratitude to Prof. Mitch Smith, Prof. Robert E. Maleczka, and Prof.

Babak Borhan for serving on my committee and for all their suggestions.

Thanks to Dr. Daniel Holmes and Mr. Kermit Johnson for their assistance in NMR,
and eSPeCially for allowing me to reserve extended time slots to perform the kinetic
e"‘pefilllcarlts. A special thank is due Dr. Richard Staples in the crystallography division. I
am thankful to Bob Rasico, Melissa Parsons, and Bill Flick for their help in the general
maintenance of the lab. I also want to thank Scott Bankrofi in the glass blowing shop,

0’“ Geissenger and Diane Karsten in the stockroom, Glenn Wesley and Tom Bartlett in

vi

the machine shop, and Scott Sanderson and Dave Cedarstaff in the electronics shop.
Karen Maki, Beth McGaw, Cindy Sanford in the Business office and Nan Murray,
Wendy Tsuji, Steve Poilios, Debbie Roper, Lisa Dillingharn in the Graduate office were

always very supportive and I thank them all.

In the process of working on one of my projects, and also in writing this thesis, I have
received generous assistance from my colleague Dr. Eyal Bemea. He deserves a special
thank you. I am also grateful to all the previous and present Odom group members:
Yahong, Jim, Bala, Kapil, Supriyo, Doug, Steve, Sameer, and Kevin(s) for their support.
I also want to mention all the undergraduates with whom I’ve worked in this lab. I’ve

really enjoyed my experience working with all of you.

I acknowledge my family for support and inspiration. Especially, my mother and
sister Apaxajita for all of your loving support. I also like to thank all my fiiends in and
outside East Lansing. Finally, the patience, inspiration, and encouragement of my

huSbflnd, Ujjal, have been crucial to complete this thesis.

Sanjukta Banetjee
East Lansing, Michigan

vii

TABLE OF CONTENTS

List of Tables ................................................................................................................... xi
List of Figures ................................................................................................................. xv
List of Schemes ............................................................................................................ xviii
List of Abbreviations ..................................................................................................... xxi
Hydroamination of alkynes ...................................................................................... 1

1.1 Introduction ....................................................................................................... 1

1.2 Hydroamination with alkali and alkaline earth metals ...................................... 4

1.3 Hydroamination with transition metals (Group 3 and 5) .................................. 6

1.4 Hydroamination with late transition metals ...................................................... 8

1.5 Hydroamination with lanthanides and actinides ............................................. 13

1.6 Hydroamination with Group 4 metal complexes ............................................ l7

1 .6.1 Hydroamination of alkynes with Zirconium ................................................... 17

l .6.2 Hydroamination of alkynes with Titanium ...................................................... l9

1 .6.3 Research in the Odom group ........................................................................... 25

1.7 Concluding Remarks ....................................................................................... 29

1-8 References ....................................................................................................... 30
Hydrohydrazination of alkynes with monosubstituted hydrazines ................... 34

2-1 Introduction ..................................................................................................... 34
2.1.1 Hydrohydrazination with Titanium ................................................................. 35

2.1.2 Hydrohydrazination with Cobalt ..................................................................... 41

2.1.3 Hydrohydrazination with Manganese .............................................................. 45

viii

2.1.4 Hydrohydrazination with Palladium ................................................................ 46

2.1.5 Hydrohydrazination with Zinc ......................................................................... 46
2.2 Synthesis of NH-indoles .................................................................................. 50
2.3 Aim of the current project ............................................................................... 51
2.4 Results and Discussion .................................................................................... 52
2.5 Concluding Remarks ....................................................................................... 66
2.6 Experimental ................................................................................................... 67
2.7 References ....................................................................................................... 87
Iminohydrazination of alkynes: scope, mechanistic investigation, and
applications towards pyrazole synthesis ............................................................... 91
3 . 1 Introduction ..................................................................................................... 91
3 .2 Results and Discussion .................................................................................... 94
3.2.1 Iminohydrazination Results ............................................................................. 94
3.3 Mechanistic Investigation ............................................................................. 101
3.3.1 Pathway via 1,2-insertion .............................................................................. 101
3.3.2 [2 + 2]-cycloaddition mechanism .................................................................. 102
3.3.3 Kinetic studies ............................................................................................... 109
3.3.4 Overall mechanism for Iminohydrazination reaction .................................... 118
3.3.5 Experimental observations on regioselectivities ........................................... 1 18
3.4 Applications of the Iminiohydrazination reaction towards the synthesis
of pyrazoles ................................................................................................... 122
3.4.1 Background information ................................................................................ 122
3.4.2 Results and Discussion .................................................................................. 123
3‘5 Multicomponent Coupling Reactions of alkynes,
monosubstituted hydrazines, and isonitriles .................................................. 130
3‘6 Concluding Remarks ..................................................................................... 136
3-7 Experimental ................................................................................................. 137
3'8 References ..................................................................................................... 166

Synthesis or Vanadium(V) hydrazido(2-) thiolate imine

all“Ride complexes ............................................................................................... 169

4-1 Introduction ................................................................................................... 169

4-2 Hydrazido versus isodiazene bonding in MNNRz complexes ...................... 171
ix

4.3 Vanadium(V) hydrazido(2—) complexes ....................................................... 173

4.4 Titanium hydrazido(2—) complexes .............................................................. 177
4.5 Aim of the current project ............................................................................. 183
4.6 Results and Discussion .................................................................................. 184
4.7 Concluding Remarks ..................................................................................... 189
4. 8 Experimental ................................................................................................. 1 90
4.9 References ..................................................................................................... 201
Appendix
A Crystallographic information ........................................................................ 205
B Kinetic reaction plots .................................................................................... 303
C 1H and 13C NMR spectra .............................................................................. 312

Table 2.1
Table 2.2
Table 2.3
Table 3.1
Table 3.2
Table 3.3
Table 3.4

Table 3.5

Table A1 . 1

Table A1 ,2

Table A1 .3
Table A1 ,4
Table A1 .5

Table Al.6

Table A1.7

LIST OF TABLES

Hydrohydrazination of alkynes with phenylhydrazine ........................... 58
Hydrohydrazination with substituted phenylhydrazines ................................ 62
Hydrohydrazination with diynes and enyne ................................................. 65
Examples of alkyne Iminohydrazination ................................................ 98
Rate Constants and conditions for kinetic experiments ........................ 114
Observed rate constant vs catalyst concentration ................................. 1 17
Iminohydrazination of phenylacetylene by different catalysts ............. 120
Effect of p-substituents on arylhydrazine on pyrazole formation ......... 128
Crystal data of Hzenp (4) ...................................................................... 205

Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Hzenp. U(eq) is defined as one third
of the trace of the orthogonalized UIJ tensor ......................................... 206

Bond lengths (A) and angles (°) for Hzenp .......................................... 207

Anisotropic displacement parameters (A2 X 103) for Hzenp. The
anisotropic displacement factor exponent takes the form:

—2pi2 [h2 a*2U” +...+2hka*b*U12] ........................................... 211
Hydrogen coordinates (X 104) and isotropic displacement parameters

(A2 X 103) for Hzenp ............................................................................ 212
Torsion angles (°) for Hzenp ................................................................. 213
Hydrogen bonds (A) and angles (°) for Hzenp ..................................... 214

xi

Table A2.1

Table A2.2

Table A2.3

Table A2.4

Table A2.5

Table A3.1

Table A3.2

Table A3.3

Table A3.4

Table A3.5

Table A4.1

Table A4.2

Table A4.3

Crystal data for Ti(bap)(NMe2)3 (28) ................................................... 215

Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Ti(bap)(NMe2)3. U(eq) is defined as one

third of the trace of the orthogonalized UlJ tensor ................................ 216
Bond lengths (A) and angles (°) for Ti(bap)(NMe2)3 .......................... 217

Anisotropic displacement parameters (A2 X 103) for Ti(bap)(NMe2)3.
The anisotropic displacement factor exponent takes the form:

-2pi2 [hza *2 U 1+. ..+2hka*b*U ] ............................................ 219
Hydrogen coordinates (X 104) and isotropic displacement parameters

(A2 x 103) for Ti(bap)(NMe2)3 ............................................................ 220
Crystal data for Ti(NNMe2)(dap)(nacnac) (36) .................................... 222

Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Ti(NN Me2)(dap)(nacr_1ac). U(eq) is defined
as one third of the trace of the orthogonalized UIJ tensor ..................... 223

Bond lengths (A) and angles (°) for Ti(NNMe2)(dap)(nacnac) ............ 224

Anisotropic displacement parameters (A2 X 103) for
Ti(NNMe2)(dap)(nacnac). The anisotropic displacement factor
exponent takes the form: -2 pi2 [h2 a"‘2 U“ +...+ 2 h k a* b* U12] 227

Hydrogen coordinates (X 104) and isotropic displacement parameters
(A2 X 103) for Ti(NNMe2)(dap)(nacnac) ............................................. 228

Crystal data for Ti2(dap)3(NNMe2)2(NHNMe2) (37) .......................... 231

Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 x 103) for Ti2(dap)3(NNMe2)2(NHNMe2). U(eq) is
defined as one third of the trace of the orthogonalized UIJ tensor ........ 232

Bond lengths (A) and angles (°) for Ti2(dap)3(NNMe2)2(N HNMez)" 23 3

xii

 

Table A4.4

Table A4.5

Table A4.6

Table A5.1

Table A5.2

Table A5.3

Table.A5.4

Table A5.5

Table A5.6

Table A6.1

Table A6.2

Table A6.3

Table A6.4

Anisotropic displacement parameters (A2 X 103) for
Ti2(dap)3(NNMe2)2(NHNMe2). The anisotropic displacement factor

exponent takes the form: —2 pi2 [h2 a"‘2 U11 +...+ 2 h k a* b* U12]... 245

Hydrogen coordinates (X 104) and isotropic displacement parameters

(A2 x 103) for Ti2(dap)3(NNMe2)2(NHNMe2) ................................... 247
Torsion angles (°) for Ti2(dap)3(NNMe2)2(NHNMe2) ........................ 249
Crystal data for 3-mesitylpyrrole (43) .................................................. 259

Atomic coordinates (X 104) and equivalent isotropic displacement
103) for 3-mesitylpyrrole. U(eq) is defined as one

third of the trace of the orthogonalized U” tensor ................................ 260
Bond lengths (A) and angles (°) for 3-mesitylpyrrole .......................... 261

2
parameters (A X

Anisotropic displacement parameters (A2 X 103) for 3-mesitylpyrrole.
The anisotropic dilsplacement factor exponent takes the form:

-2piz [hza *2 U] 1+. ..+2hka*b*U 2] ............................................ 263
Hydrogen coordinates (X 104) and isotropic displacement parameters

(A2 X 103) for 3-mesitylpyrrole ............................................................ 264
Torsion angles (°) for 3-mesitylpyrrole ................................................ 265

Crystal data for Ti(dap3'"‘es)2(NMe2)2 (45) ........................................ 266

Atomic coordinates (X 104) and equivalent isotropic displacement

parameters (A2 X 103) for Hzenp. U(eq) is defined as one third

of the trace of the orthogonalized UlJ tensor ......................................... 267
. 3—mes

Bond lengths (A) and angles (°) for T101511) )2(NM62)2 ................ 269

Anisotropic displacement parameters (A2 X 103) for

Ti(dap3-mes)2(NMe2)2. The anisotropic displacement factor exponent
takes the form: -2 pi2 [112.1112 U” +...+2 hka* 13* U12] ................... 279

xiii

 

Table A6.5

Table A6.6

Table A7.1

Table A7.2

Table A7.3

Table A7.4

Table A7.5

Table A7.6

. 4 . . .
Hydrogen coordinates (X 10 ) and lSOtI'OplC displacement parameters

(A2 x 103) for Ti(dap3-mes)2(NMe2)2 .................................................. 281
. . 3-mes

Torsron angles (°) for T1(dap )2(NMe2)2 ...................................... 283

Crystal data of V(NNMe2)(TIP)(dmpe)(I) (49) .................................... 288

Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 x 103) for V(NNMe2)(TIP)(dmpe)(I). U(eq) is
defined as one third of the trace of the orthogonalized UlJ tensor ........ 289

Bond lengths (A) and angles (°) for V(NNMe2)(TIP)(dmpe)(I) .......... 290

Anisotropic displacement parameters (A2 X 103) for
V(NNMe2)(TIP)(dmpe)(I). The anisotropic displacement factor
exponent takes the form: —2 pi2 [h2 a"‘2 U11 +...+ 2 h k a* b* U12]... 296

Hydrogen coordinates (X 104) and isotropic displacement parameters

(A2 X 103) for V(NNMe2)(TIP)(dmpe)(I) ............................................ 297
Torsion angles (°) for V(NNMe2)(TIP)(dmpe)(I) ................................ 299

 

i__

 

LIST OF FIGURES

“Images in this dissertation are presented in color”

Figure 1.1

Figure 1.2

Figure 2.1

Figure 2.2

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6
Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 4.1

Scandium-based metal complexes for intramolecular hydroamination 6

Tantalum catalysts (neutral and cationic) for intramolecular
hydroamination ......................................................................................... 7

ORTEP representation (50% probability level) of Hzenp (4) ................ 53

Synthesis of Ti(enp)(NMe2)2 (5) and comparison with
Ti(dap)2(NMe2)2 (1) ............................................................................... 54

Solid-state structure of Ti(NMe2)3(bap) (28) from X-ray diffraction... 97

Structure of hydrazido(2—) complex 36 from X-ray diffraction. .......... 105

Possible resonance forms of 36. (For simplicity, the other ligands
are not shown) ....................................................................................... 106

ORTEP representation of Ti2(dap)3(u2:nl,nz—NNMe2)2(u1 :nl-NHNMez)

(37) at 50% probability level ................................................................ 108
Representative plot for the catalysis with Ti(dap)2(NMe2)2 (1) .......... 110
Representative plot for the catalysis with 36 ........................................ 112

Representative plot for reaction of 36 with 1,1 -dimethylhydrazine ..... 113

Representative plot for the catalysis with 10 mol% of 36 and Hdap 115

Dependence of kobs on catalyst concentration ..................................... 117

ORTEP representation of 3-mesity1pyrrole (43) .................................. 132
. . 3-mes

ORTEP representation of T1(dap )2(NMe2)2 (45) ........................ 134

Hydrazido(2—) vs isodiazene resonance forms ..................................... 171

XV

Figure 4.2

Figure 4.3

Figure 81.1

Figure 81.2

Figure 81.3

Figure 82.1
Figure 82.2

Figure 82.3
Figure 83.1
Figure 83.2

Figure 83.3
Figure 84.1
Figure 84.2
Figure 84.3

Figure 85.1
Figure 86.1
Figure 86.2

Figure 86.3

Figure C]

Figure C.2

ORTEP representation of the cationic part in 49 .................................. 187

(a) Hydrazido(2—) vs isodiazene resonance forms in vanadium

complex. (b) Structure of 52 ................................................................. 188
Kinetic plot for Run 1 with 10% Ti(dap)2(NMe2)2 (1). ....................... 303
Kinetic plot for Run 2 with 10% Ti(dap)2(NMe2)2 (1). ....................... 304
Kinetic plot for Run 3 with 10% Ti(dap)2(NMe2)2 (1). ....................... 304
Kinetic plot for run 1 with 10% 36 ....................................................... 305
Kinetic plot for run 2 with 10% 36 ....................................................... 305
Kinetic plot for run 3 with 10% 36 ....................................................... 306
Kinetic plot for run 1 with 36 + 10 MezNNHZ reaction. ...................... 306
Kinetic plot for run 2 with 36 + 10 MezNNHz reaction ....................... 307
Kinetic plot for run 3 with 36 + 10 MezNNHz reaction ....................... 307
Kinetic plot for run 1 with 10% 36 + 10% Hdap reaction .................... 308
Kinetic plot for run 2 with 10% 36 + 10% Hdap reaction .................... 308
Kinetic plot for run 3 with 10% 36 + 10% Hdap reaction .................... 309
Kinetic plot for run 1 with 10% 37 ....................................................... 309
Kinetic plot with 15% Ti(dap)2(NMe2)2 .............................................. 310
Kinetic plot with 5% Ti(dap)2(NMe2)2 ................................................ 310
Kinetic plot with 2.5% Ti(dap)2(NMe2)2 ............................................. 31 1
1H and 13C NMR spectra of compound 2. ........................................... 312
1H and '3C NMR spectra of compound 4. ........................................... 313

xvi

Figure C.3

Figure C.4

Figure C.5

Figure C.6

Figure C.7

Figure C.8

Figure C.9

Figure C.10

Figure C.11

Figure C.12

Figure C.13

Figure C.14

Hymafi

Figure C.16

Figure C.17

mwmcm

Figure C.19

Figure C.20

1H and 13C NMR spectra of compound 5. ........................................... 314

1H and 13C NMR spectra of compound 7. ........................................... 315
1H and 13C NMR spectra of compound 13 and 14 ............................... 316
1H and 13C NMR spectra of compound 15. ......................................... 317
1 13

H and C NMR spectra of compound 17. ......................................... 318
1 13

H and C NMR spectra of compound 20. ......................................... 319
1H and 13C NMR spectra of compound 21. ......................................... 320
1H and 13C NMR spectra of compound 24. ......................................... 321
1H and 13C NMR spectra of compound 25. ......................................... 322
1H and 13C NMR spectra of compound 35. ......................................... 323
1H and 13C NMR spectra of compound 38. ......................................... 324
1 13

H and C NMR spectra of compound 39. ......................................... 325
1H and 13C NMR spectra of compound 40. ......................................... 326
l 13

H and C NMR spectra of compound 41. ......................................... 327
l 13

H and C NMR spectra of compound 42. ......................................... 328
1 13

H and C NMR spectra of compound 44. ......................................... 329
1 13

H and C NMR spectra of compound 45. ......................................... 330
1 13

H and C NMR spectra of compound 46. ......................................... 331

xvii

Scheme 1.1

Scheme 1.2

Scheme 1.3

Scheme 1.4

Scheme 1.5

Scheme 1.6

Scheme 1.7

Scheme 1.8

Scheme 1.9

Scheme 1.10

Scheme 1.1 1

Scheme 1.12

Scheme 1.13

Scheme 1.14

Scheme 2.1

Scheme 2.2

Scheme 2.3

Scheme 2.4

LIST OF SCHEMES

Hydroamination of alkenes and alkynes generating amines ..................... 2
Thermodynamics for addition of ammonia and ethylamine to ethylene .. 3
Indole synthesis via hydroamination of vinylarenes by alkali metals ...... 4

Mechanistic pathway for hydroamination of alkynes by lanthanides ..... 14

Intermolecular hydroamination with actinides ....................................... 15
Mechanistic pathway of hydroamination of alkynes by actinides .......... l6
Mechanistic pathway for catalytic hydroamination of alkynes .............. 18
Synthesis of first titanium-based hydroamination catalyst ..................... 20
Synthesis of (fl-monomorine ................................................................. 21
Intermolecular hydroamination of alkyne with szTiMez .................... 22
Synthesis of (it-amino esters via hydroamination pathway ..................... 25
Synthesis of Ti(dpma)(NMez)2 .............................................................. 27
Proposed mechanistic pathway for hydroamination of alkyne ............... 27
Synthesis of Ti(dpm)(NMe2)2 ................................................................ 28

Titanium-catalyzed hydrohydrazination of alkynes and synthesis of
N-substituted indole ................................................................................ 35

Proposed mechanistic pathway for the hydrohydrazination reaction
using 1,1-disubstituted hydrazines .......................................................... 37

Cp-based titanium-catalyzed hydrohydrazination of alkynes and
synthesis of substituted N—methylindoles ................................................ 38

Cp—based titanium-catalyzed hydrohydrazination of alkynes and
synthesis of substituted N-methyltryptamines ........................................ 38

xviii

 

Scheme 2.5

Scheme 2.6

Scheme 2.7

Scheme 2.8

Scheme 2.9

Scheme 2.10

Scheme 2.11

Scheme 2.12

Scheme 2.13

Scheme 3.1

Scheme 3.2

Scheme 3.3

Scheme 3.4

Scheme 3.5

Scheme 3.6

Scheme 3.7

Scheme 4.1

Scheme 4.2

Scheme 4.3

Scheme 4.4

Synthesis of tryptamine derivatives by aryloxo—based Ti-catalyst ......... 40
Proposed mechanism for Co-catalyzed hydrohydrazination of olefin.... 42

Synthesis of NH-indole by zinc salts ...................................................... 47

Synthesis of pyrazoline and pyrazole by Zn(OTf)2-catalyzed

hydrohydrazination ................................................................................. 48
Synthesis of pyridazinones via hydrohydrazination using ZnC12 .......... 49
Synthesis of Hzenp (4) ............................................................................ 53
Reaction of 2-hexyne with phenylhydrazine catalyzed by 5 .................. 56

Hydrohydrazination of 5-chloropent-1-yne with phenylhydrazine ........ 61
Possible pathways to 24 and 25 .............................................................. 64
Ugi 4-component reaction ...................................................................... 92
Possible 1,2-insertion pathway for the iminohydrazination reaction 101

Possible mechanistic pathway of iminohydrazination by l for
Entry 1 in Table 3.1 .............................................................................. 103

Synthesis of pyrazole from 4-amino-l-azabutadienes .......................... 122

Synthesis of N-phenyl-5-n-butylpyrazole and

N-phenyl-3 -n-buty1pyrazole .................................................................. 1. 24
Possible mechanistic pathways for the pyrazole formation .................. 125
Synthesis of 3-mesitylpyrrole (43) ....................................................... 131

Synthesis of a vanadium hydrazido(2—) complex with O(SCH2CH2)22-

 

as co-ligand ........................................................... 175
Synthesis of titanium hydrazido(2—) complexes ................................... 180
Synthesis of titanium-hydrazido(2—) complexes with

different fac-N3 donor ligands .............................................................. 181

Synthesis of titanium hydrazido(2—) complexe from imido complexesl 82

xix

Scheme 4.5 Synthesis of V(NNMe2)(OAr)(TIP) (46) (Ar = 2,6-Pri2C6H3) ........... 184

Scheme 4.6 Synthesis of cationic hydrazido(2—) complexes ................................... 186

XX

bap
BOC
bpy
But-bpy
COD
dap
DEAD
DIPP
DMAP
dpm
szpm
dpma
dppf
GC/F ID
GCMS
Hzenp
LLCT
Nacnac
RT
TBS
triphos

Tosyl

LIST OF ABBREVIATIONS

bis-2,5-(N, N—dimethylaminomethyl)pyrrolyl
tert-butyloxycarbonyl

2,2'-bipyridine
4,4'-di-tert—butyl-2,2'-bipyridine
cyclooctadiene
2-((dimethylamino)methy1)pyrrolyl
di-tert-butylazodicarboxylate
di-iso-propylphenyloxide
N,N-dimethylaminopyridine
Dipivaloylmethanato
5,5—dimethyldipyrrolylmethane
N,N-di(pyrrolyl-a—methyl)-N-methylamine

1 ,1 '-bis(diphenylphosphino)ferrocene

Gas Chromatography Flame Ionization Detector
Gas Chromatography Mass Spectroscopy
Nl ,Nz-bis((1H—pyrrol-2-y1)methyl)-NI ,Nz-dimethylethane-l ,2-diamine
Ligand to ligand charge transfer
[N(But)CHCHC(Bun)N(NMe2)-k2N]

room temperature

tert-butyldimethylsilyl

1 , 1 ,1 -tris(diphenylphosphinomethyl)ethane

p—tolylsulfonyl

xxi

n. 4“... 4.... .- A A

CHAPTER 1

Hydroamination of alkynes

The primary focus of this thesis is the development of hydrohydrazination reactions
for alkynes and their applications towards the synthesis of heterocycles.
Hydrohydrazination is the formal addition of hydrazine to unsaturated C—C bonds
resulting in hydrazones or substituted hydrazines. The first example of
hydrohydrazination was reported in 2002 by our group; since, it has been explored by us
and other research groups. On the other hand, hydroamination, where amines (instead of
hydrazines) are added across the C—C unsaturation, has been more extensively studied
since its discovery in the 1950’s. Because hydroamination reactions are closely related to
hydrohydrazination, and more prominent in the literature, they will be discussed as an
introduction in this chapter. Hydrohydrazination of alkynes and its synthetic applications

will be discussed in subsequent chapters.

1.1 Introduction

Hydroamination is the formal addition of an N—H bond across C—C unsaturation

resulting in nitrogen-containing products such as amines, imines, or enamines (Scheme

1.1).1 These molecules are important building blocks of different biologically active

compounds (e.g. alkaloids, amino acids, vitamins), fine chemicals, and pharmaceuticals.
Hydroamination is an efficient way to synthesize amines, imines, or enamines with 100%
atom economy. While hydroamination of alkenes generates amines, alkynes produce
imines and enamines, which can also be reduced to amines if desired. Therefore,

hydroamination provides an efficient route to synthesize amines, which are produced in
several million tons per year industrially. In addition to this, 80% of the pharmaceutical

products are composed of C—N bonds.

Scheme 1.1 Hydroamination of alkenes and alkynes generating amines

R3
3 \N-R4
_ + NH = ,—<
1‘ '7 2 R1 R2

amine

R R

enamlne
R _ R2 + R3NH2 = R?
l N-H
3 ‘ L

‘ (NR / R1 R2
amine
R1 R2 H

2

 

 

imine

However, hydroamination usually has a high activation energy, primarily due to
repulsion between the lone pair on nitrogen and n—electrons of the C—C unsaturated bond.

In addition to that, since the uncatalyzed reactions exhibit a negative entropy change,

increasing the temperature makes the forward reaction thermodynamically less favorable

(Scheme 1.2). To overcome all these barriers, a suitable catalyst design is necessary.

As illustrated in Scheme 1.2, the addition of ammonia or simple amines to ethylene is

. . 3 . . . .
slightly exothermic or thermoneutral. Semiempirical calculations have shown that the
addition of ammonia to acetylene is even more exothermic than ethylene by

approximately 63 kJ mol_].I As a consequence, while hydroamination of alkynes have

been extensively explored, that of unactivated alkenes is still a challenge.

Scbeme 1.2 Thermodynamics for addition of ammonia and ethylamine to ethylene

AG° = —14.7 kJ mol—1

 

 

 

NH2 _1
= + NH3 _/ AH° =—52.7 kJ mol
AS° = —127.3 J mol‘1 K‘1
,__ —1
_ + NHEt AG — 33.4 kJ mol 1
— EtNH2 AH° = —78.7 kJ mol—

AS° = —152.2 J mor1 K‘1

Over the last few decades, extensive research efforts have been directed towards the
hydroamination reaction. Hydroamination of alkynes is known with different metals
Spar“ling the periodic table from alkali metals to transition and f—block metals. In the
following sections, intermolecular hydroamination (mainly) with some 0f the

r
epl.eSentative metals will be discussed with an emphasis on Group 4 metal catalysis.

1.2 Hydroamination with alkali and alkaline earth metals

The first well-recognized example of alkali metal catalyzed hydroamination was

reported in 1954 by Howk et al.4 They demonstrated that ammonia adds to ethylene in

the presence of metallic sodium at about 200 °C and 1000 bar in an inert medium
forming ethyl-, diethyl-, and triethylamine in 70% total yield. Alkali metal hydrides such

as NaH and LiH have also been found to be equally active. Aniline is converted to N-
ethylaniline by Na or NaNH2 at 250—300 °C and 50—200 bar. It is interesting to note that

a few late alkali metal amides such as rubidium and cesium amides catalyze the

amination of ethylene at considerably milder conditions (80—1 10 °C and 90—120 bar) in
moderate yields.5’6 Since milder conditions are used in the case of alkali metal amides,
mOI10--alkylated amines are formed selectively.

Apart from the inorganic salts of alkali metals, organic salts have also been found to

be active for hydroamination of alkynes with amines. For example, BunLi7 and KOBut8

serve as active precatalysts for the addition of amines to alkenes (ethylene or styrene).

Benet has expanded this protocol towards the synthesis of indoles by hydroamination of

Styrene derivatives followed by oxidation (Scheme 1.3).9

Sch eme 1.3 Indole synthesis via hydroamination of vinylarenes by alkali metals

 

 

l \ \ n
// 1) 0.1 equw. Bu Ll
X THE—30 °c I \ Pd/C m
'0' ; >
R’ 2) KOBut // N HCOONH4 // N
NH2 X k: 120°C X h'

toluene, 135 °C

Knochel has shown that CsOH-HZO is an effective precatalyst for the addition of
secondary aromatic or heterocyclic amines to phenylacetylene in NMP (N-

methylpiperidine) leading to enamines. I 0

There are only a few examples in the literature of hydroamination catalyzed by

alkaline earth metals. Hill first reported Ca-catalyzed intramolecular hydroamination of

aminoalkene. A B-diketiminato—based Ca complex, [{HC-(C(Me)2N-2,6-Pri2C6H3)2}Ca-
{N(SiMe3)2}-(THF)], was used as the catalyst.” More recently, Roesky et al. has
reported a different complex with Group 2 metals (M = Ca, Ba, Sr),
[{(Pri)2ATI}M{N(SiMe3)2}(THF)2], where (Pri)2ATI = N-isopropyl-2-(isopropylarnino)
troponiminate.12’l3 These complexes are active for intramolecular hydroamination of

aminoolefins. It is interesting to note that the reactivity decreases with increasing atomic
radius of the metal. Although the elements in this group are not well-explored for
hydroamination reactions, they are potentially important for industrial use as they are

inexpensive and environmentally benign.

1.3 Hydroamination with transition metals (Group 3 and 5)

Roesky and co-workers have reported that mono- and bis(N-iso-propyl-2-(iso-

propylamino)troponiminato) yttrium amides, [(Pri)2ATI]mY[N(SiMe3)2]n (where m =

1-2; n = 3—m), are effective for intramolecular hydroamination of alkynes.14 Schafer has

described scandium-catalyzed hydroamination of aminoalkynes and aminoalkenes. Both
neutral and cationic complexes were synthesized using aldiminato- and diketiminato-

ligands (Figure l.l). The key to this activity is the small ionic radius of scandium and the

. . . . . . . . 15 . . .
availability of an open coordination Site on the cationic complex. Further investigation

in this field has involved the synthesis of both neutral and cationic complexes of

scandium and yttrium with bidentate amidinate and tetradentate triamine-arnide

ligands. 16 The activity of the catalysts depends on the nature of the ancillary ligands.

Figure 1.1 Sc-based metal complexes for intramolecular hydroamination.

 

R2
R‘Q
_N R1
Sc-CHZSiMezPh
o
t
Bu
Ar = 2
R1 = Pr’, R2 = H
R = CH3. ‘CH33(C6F5)3 R1 = R2 = H

 

 

Among the group 5 metals, Bergman has shown several tantalum imido complexes

(both neutral and cationic) that are efficient catalysts for intermolecular hydroamination

of alkynes and alkenes (Figure 1.2).17 Different amido- and imido-vanadium complexes

have shown moderate reactivity towards intermolecular hydroamination of alkynes with

. . l8 . . .
aromatic ammes. These catalysts generate Markovnikov imine products almost

exclusively.

Figure 1.2 Tantalum catalysts (neutral and cationic) for intramolecular hydroamination.

t

Ph—\ t Bu _\ t P h—\® t e
rTaZN—Bu l/TaZN-Bu TaZN-Bu 8(06F5)4
Ph 1‘ t PhJ
Ph BU Bu

1.4 Hydroamination with late transition metals

In contrast to early transition metals and f-block elements, late transition metals
provide alternative catalytic systems that are less air and moisture sensitive. They are also

less oxophilic and often more functional group tolerant. Until 1999, hydroamination was
. l9 . 20 . .

only known With mercury and thallium among the late tranSition metals. However

these two are toxic. Therefore, the search for more environmentally benign catalytic

systems was necessary.

Wakatsuki and co-workers first reported an efiicient late transition metal catalyst,

RU3(CO)12, for intermolecular hydroamination?‘ Only 0.1 mol% of the catalyst was

used in the presence of 0.3 mol% acidic additive NH4PF6 for the hydroamination of
terminal alkynes with aniline. Moreover, the reactions can be carried out in open air

under solvent-free conditions.

More recently, Takai has expanded this methodology towards the synthesis of indene

derivatives in a one-pot, two-step procedure; hydroamination was followed by C—H

activation with [ReBr(CO)3(THF)]2 and coupling with ethyl acrylate.22 A cationic

complex, [(PCy3)2(CO)(CH3CN)2RuH]+BF4_, also has been used for intermolecular

cyclization of amine and alkynes. The resulting quinoline products are obtained in 43—

94% yield.23

The first example of rhodium-catalyzed intermolecular hydroamination of terminal

alkynes with aniline was reported by Beller in 2001.24 The cationic Rh(l) catalyst,

«F3

’4, '
f;

.l-H

“In
.

a
n
.
..
s“

Rh(COD)2BF4/3 PCy3 in THF was found to be very active for such transformations with

up to 99% yield under very mild conditions (room temperature) and without any acid or
base (Equation 1.1). The generated imines were further converted to secondary amines in
situ by organolithium reagents. This catalyst is less oxophilic, nontoxic, and easy to

handle compared to early transition metal catalysts.

1.5% [Rh(COD)2]BF4 NR
R—E + R'NH2 = R (1 .1)
4.5% PCy3

 

R = n-hexyl, n-butyl, C6H5 yields: 55—99%
R' = C6H5, 2-Me-06H4, 4-Me-CGH4,

4-OMe-C6H4, 3-F-C6H4, 4-CI-CGH4

More recently, different Rh(I) and Ir(l) complexes containing bidentate phosphine-

pyrazolyl ligands having the molecular formula [M(R2PyP)(COD)]BPh4 (R = Me, Pri,
Ph; M = Ir, Rh) (where COD = cyclooctadiene), [lr(R2PyP)(COD)]BPh4 (R = Me, Pri),

and [M(R2PyP)(CO)Cl] (R = Me, Pri, Ph, M = Ir, Rh) were reported for intramolecular

hydroamination of alkynes. Cationic Ir complexes with COD ligands are more active than
CO ligands. Moreover, the neutral complexes are inactive for intramolecular

hydroamination. Another interesting observation is that the Rh(I) cationic complexes are

less effective than their Ir(I) analogues.25

Among the noble metals, a few Au(I) and Au(III) complexes are known to be active

for hydroamination of alkynes. In 1987, Utimoto reported NaAuCl4-2HzO-catalyzed

hydroamination of S-alkynylamines to form tetrahydropyridine derivatives (Equation

1.2).26’ 27

He also expanded this methodology towards the synthesis of indoles (Equation

1.3).28 Marinelli expanded the scope of this reaction by using an ethanol/water mixed

29
solvent system.

 

 

NH2 5% NaAuCl4-2H20 LNjA’mBHfi

= (12)

% CH3CN, reflux, 1 h

nC5H13 80%

/ Bun H

/ 5% NaAuCI4-2H20 N
= / EU" (1.3)

NH2 THF, 25 C, 2 h

87%

Acid-promoted intermolecular hydroamination of terminal and internal alkynes have

been carried out with (PPh3)Au(CH3) to generate imines (Equation 1.4).30 Both aryl and

alkyl, terminal and internal alkynes have been used. Different primary aromatic amines
(electron-rich, electron-deficient, and sterically hindered) are effective in this reaction,

however, alkylamines are not. More recently, a new porphyrin-based Au(III) catalyst was

. . . I
introduced for hydroamination of alkynes.3

Br
0.1% (PPh3)Au(CH3) 0
¢ 3' 050/ H PW o
O - o 3 12 4o CH3
+ o > (1-4)
H2N 70 0,211

94%

 

l0

Surprisingly, the reaction of phenylacetylene with aniline in the presence of catalytic
AgBF4/HBF4 produces 1,2—dihydroquinoline derivatives instead of imine products
(Equation 1.5). In this case, the products are formed by hydroamination followed by

hydroarylation.32 Ag-catalyzed hydroamination are also applied to synthesize pyrroles.33

 

/

\ / \ NH2 catAgBF4

l \. + l \, (1.5)
’ R ’ R' cat. HBF4

140 °C

 

R = H, p-Me, p-F
R' = p—Me, p-Cl, p-F YIBIdI 60—88%

In addition, a combination of both Au/Ag-catalyzed microwave-assisted

hydroamination of alkynes with amines was reported where 1,2-dihydroquinolines were

obtained as the final products (Equation 1.6).34

 

I \ NH2 1
X122 5% AuCI3/AgOTf 11 R H
N N
15% NH PF \ \
+ 4 6 > R2_: R1+ R2_:_ R1 (1.6)
CH3CN, 150°C / / / /
:——R microwave irradiation R1 R1

Yamamoto described the formation of pyrrolidine and piperidines by intramolecular

hydroamination of amines or sulfonyl amides, bearing a terminal allene group using Pd

catalyst. This involved the addition of an M—H bond across an allenic double bond.35 Pd-

catalyzed hydroamination of allenes was reported for the synthesis of allylic amines.36

The same group showed an efficient stereoselective hydroamination of conjugated

enynes in the presence of a palladium catalyst (Equation 1.7).37 The reactions only

occured in the presence of a phosphine-based ligand.

[(n3—C3H5)PdCI]2 R1

1 dppf, CH3C02H )1 R 1
E—-\{ +R\NH ‘ R H /R (17)
1 THF, 80°C N

R \

 

l

R = Me, hexyl, SiMe3

R1 = PhCH2, —CHZCH=CH2

dppf = 1,1'—bis(diphenylphosphino)ferrocene

Intermolecular hydroamination of aminoalkynes using Group 7—12 metals has been
reported. For example, [Cu(CH3CN)4]PF6, Zn(CF3SO3)2, and [Pd(triphos)](CF3SO3)2
(where triphos = 1,1,l-tris(diphenylphosphinomethyl)ethane) have been used, and the

products are substituted pyrrolidines and piperidines.38

12

1.5 Hydroamination with lanthanides and actinides

Marks and co-workers discovered lanthanide-based catalysts effective for both intra-

and intermolecular hydroamination of alkenes and alkynes.39 The f-block elements are

quite different in their activity towards activation of unsaturated organic substrates (C=C
and CEC activation in particular) and heteroatom cyclization due to their high

electrophilicity, large atomic radius, and nondissociative ancillary ligation. Complexes

having the structure Cp'anCH(SiMe3)2 (Ln = Sm, Cp' = nS-M65C5) and

MezsiCp"2LnCH(SiMe3)2 (Ln = Nd, Sm, Lu; Cp" = nS-Me4C5) are effective

precatalysts for both intra- and intermolecular hydroamination of alkenes, alkynes, and
dienes. However, the corresponding intramolecular processes are ~1000 times faster than
the intermolecular processes. Mechanistically, the turnover limiting step is the insertion
of C=C or CEC bonds into Ln—N bond followed by rapid protonolysis of the resulting

Ln-C bond (Scheme 1.4).

 

Scheme 1.4 Mechanistic pathway for hydroamination of alkynes by lanthanides

, g\ H,
“Si Ln— C” \ SIMe3

 

/ ,\
é‘ \SiMe3
/R
It
R'—C CH _
H2 3 R NH2
I CH2(SiMe3)2
H NHR
R. CH3 I, / 5\
'Si Ln—NHR
’ 2 [$9 CH3
R-NHZ J K:
I?! NHR 5
,, \ CH , \
Si Lnf 3 Si Ln— NHR

’ .\ R. (é

% %%CH3

2 R.
r... i R .

, KNLH R = n-propyl, n-butyl, i-butyl

. ' n , \ I _ .
I 33‘ ’x) R - SlMe3, CeH5, CH3

VCH3 Ln = Sm, Nd
R!

Intermolecular hydroamination of terminal alkynes (aliphatic and aromatic) with

primary aliphatic amines was carried out with organoactinide complexes Cp*2AcR2 (Ac

= Th, U; R = Me, HNR) developed by Eisen and co-workers.40’4l Here the

regioselectivity of hydroamination depends on the nature of the metal. While aldimine

products are obtained in good to excellent yield with the uranium complex, only poor to

moderate yields of ketimine products were observed in the case of thorium (Scheme 1.5).

Scheme 1.5 Intermolecular hydroamination with actinides

,E
Nt

_ 0.5% Cp*2UMe2 /\/\/U\H

H—_—\_\ + EtNHz 88°/
0

0.5% Cp*2UMez
H———\__ + EtNH2 10% V \/\/U\CH3

 

Cp"r = C5Me5

In general, there are considerable differences in the reactivity of 4f- (lanthanides) and
5f— (actinides) metal complexes in hydroamination reactions. In the case of actinides,
only terminal alkynes undergo reaction with amines but not internal ones. Silyl
substituent effects are minor for actinides. Hydroamination of alkenes have not been
observed with actinides. Mechanistically, for actinides, the rate-determining step is the

formation of the metal-imido complex after N—H o—bond activation followed by the
release of CH4 (Scheme 1.6). The intermediate then undergoes rapid cyclization with
alkyne to form a four-membered metallacycle. This is followed by protonolysis by amine.

The enamine product is produced along with regeneration of the metal-imido species.

The enamine product then converts into the more stable imine isomer.

 

Scheme 1.6 Mechanistic pathway of hydroamination of alkynes by actinides

Cp*2AcMe2

/ R'NH2

JK 2 CH4

 

 

 

   

* INHR‘
0" ZAC‘NHR'
NH2R'
H NR'
/ R H
H NHR' Cp*2Ac(NHR')2

   

 

 

R H
R'NHz
Cp2*Ac=NR' + R'NH2
Cp2*Ac’ /N'
X00
Cp*— - Me5C5
NHR' Cp2*Ac’ ’\
c .A / NHR' ‘c C”
92 C / R
C=CH

R'NH2

1.6 Hydroamination with Group 4 metal complexes
1.6.1 Hydroamination of alkynes with Zirconium

The earliest example of zirconium-catalyzed hydroamination appeared in the

2,

literature from the pioneering work of Bergmann in 1992.4 43 He discovered that the

zirconocene bis(amide) [Cp2Zr(NH-2,6-Me2C6H3)2] catalyzed the intermolecular

hydroamination of aromatic amines with alkynes and allenes. The reaction took place at
90-120 °C in the presence of 2—3 mol% of the catalyst. Although the catalyst seemed to
be stable under these reaction conditions, the reaction was found to be relatively slow.

While the enamine formed from diphenylacetylene was isolated in 60% yield, the

enamine formed from 2-butyne only was observed by 1H NMR. In the second case, the

product was the more stable imine isomer (Equation 1.8).

 

 

o NHAr N—Al'
R : R + A rNH2 3 mol /0 CpZZr(NHAr);= _ + 2, (1.8)
06H6, 120 °C. 13 d R R R R
R=Ph,Me R=Ph R=Me
Ar = 2,6—Me205H3 enamine imine

Although the above described zirconocene catalyst was inactive for alkene
hydroamination, it hydroaminated allene under relatively mild conditions (Equation 1.9).

The Markovnikov addition product, the imine of acetone, was isolated in 83% yield.

 

2.7 mol% CpZZr(NHAr)2 NAr

 

ArNHz + (1.9)

05H5, 90 °C, 6 (1 Me Me
83%

Ar = 2.6-Me2C6H3

A detailed kinetic study was carried out to investigate the mechanism of the above
transformation (Scheme 1.7). The catalytic cycle begins with the formation of zirconium
imido complex from the zirconocene precatalyst. This is followed by the [2 + 2]-
cycloaddition of the alkyne to form an azametallacyclobutene intermediate. Rapid
protonation by the amine generates the enamide-amide complex, which then undergoes

a-elimination of enamine to regenerate the catalytically active species.

Scheme 1.7 Mechanistic pathway for catalytic hydroamination of alkynes

 

 

 

CpZZr(NHAr)2 Cp22r=NHAr + ArNH2
NHAr Ph : Ph
[2+2]

Ar

Ph _ ’

/N Cp Zr N

Cp22r\ l 2 _
A,NH Ph Ph Ph

Ar = 2,6-Me206H3

ArNH2

l8

 

Although the reaction was limited to disubstituted alkynes and bulky aromatic
amines, this was a breakthrough in Group 4 alkyne hydroamination. Not surprisingly, this
was followed by a series of hydroamination reactions using another Group 4 element,

titanium, which are described in the next section.

More recently, Schafer has reported bis(amidate) bis(amido) zirconium complexes

(Equation 1.10), which are effective precatalysts for both intra- and intermolecular

. . 44,4
hydroamination of alkynes. 5

 

, 4(
Toluene N INEtz
JL J< + Zr(NEt) - R—(z Zr. (1.10)
N 24 O
2

2 R H heat, 14h NEt2

R = Pri, Ph. c61=5

1.6.2 Hydroamination of alkynes with Titanium

The earliest example of titanium-catalyzed hydroamination was reported by Rothwell
and co-workers.46 They showed the hydroamination of 3-hexyne with aniline using
bis(phenylamido) titanium(IV) complex (Scheme 1.8). They also reported for the first

time a structurally characterized titanium imido complex. However, the isolated imido

pyridine complex did not exhibit any reactivity towards hydroamination of 3-hexyne.

 

In 1992, Livinghouse reported hydroamination with a Cp-based (Cp =

cyclopentadiene, C5H5-) titanium complex. He showed intramolecular hydroamination

of y— and 5-aminoalkynes with 20 mol% CpTiCl3 and 40 mol% PrizNEt.47’48

Scheme 1.8 Synthesis of first titanium-based hydroamination catalyst

 

 

 

 

Py
Ar"Oz,, , Ph 2PhNH Ar"o, NHPh 291/ Ar"0m.. i
.. (TI: 2 T }Ti: ; " / iZNHPh
A, 0 Ph Ar"O NHPh Ar 0
. PY
Ar" = Pr’206H3
Ar"O,,' '/NHPh
.. (TR Ph
Ar 0 NHPh \N
Et : Et + PhNH2 f
EtJK/Et

The mechanism is very similar to that depicted by Bergman. The cycle starts with the
formation of the imido complex, followed by [2 + 2]-cycloaddition with the alkyne
forming an azametallacyclobutene intermediate. The final step involves protonation to
generate the product. Although this methodology was restricted to intramolecular

hydroamination, it did not require a sterically bulky amine. He also extended this

methodology towards the synthesis of the natural product (i)-monomorine.49 The key

step involves CpTiCl3-catalyzed hydroamination of aminoalkyne as shown in Scheme

1.9.

20

Scheme 1.9 Synthesis of (dz)-monomorine

 

0’ 0‘ 20% CpTiCl3
40% NEt3 _
THF, 25 °C
93%

   

(i)-monomorine

Another Cp-based titanium catalyst, szTi(NHPh)2, and more versatile CpZTiMez

were introduced by Doye in 1999.50 Both aryl and alkyl amines can be used in the

hydroamination with symmetrically substituted internal and terminal alkynes. The
resulting imines were either converted into ketones or reduced to amines (Scheme 1.10).
Although good yields were obtained with aryl amines and sterically demanding sec- and

tert-alkyl amines, yields were poor for less hindered n-alkyl and benzyl amines. Later, a

slightly modified Cp-based titanium catalyst, Cp*2TiMe2 (Cp* = Me5C5-), was found to
be successful for hydroamination with less hindered amines.“ A recently reported
catalyst for similar transformations involves an indenyl ligand, (Ind)2TiMe2, which is

also commonly used for intermolecular hydroamination of alkynes.52 While anti-

Markovnikov products were observed with arylalkynes, only Markovnikov products were

21

1'15

obtained with alkylalkynes and arylamines. Bergman has shown hydroamination of

. . . . . 53
allene us1ng szTlMEz as the precatalyst, and the product 13 the imine of acetone.

Scheme 1.10 Intermolecular hydroamination of alkyne with szTiMez

 

 

 

1) 3% Cp2TiMe2 Ph : Ph 1) 3% Cp2TiMe2
20, toluene, 100 °C + tomene, 100 °C NHR
Ph Ph 2) $102 R—NH2 2) LiA|H4 ph’ Ph
THF, 65 °C

In 2002, Beller developed new titanocene alkyne complexes [(Cp2Ti('r)2-
Me3SiCECSiMe3)] and [(szTi(n2-Me3SiCECPh)] for intermolecular hydroamination of

. . 54 . . . .
both terminal and internal alkynes. Excellent anti-Markovnikov select1v1ty was

observed with terminal aliphatic alkynes with tert—butylamine. The selectivity was
observed to increase depending on the steric bulk of the amine. In the reaction of aniline
with l-hexyne, the product was obtained almost to the exclusion of the anti—Markovnikov
product (Markovnikov:anti-Markovnikov = 1:99). Later, the same group introduced an
aryloxo-based titanium precatalyst for chemo- and regioselective intermolecular

hydroamination of terminal and internal alkynes with aliphatic and aromatic amines in

good to excellent yields (Equation 1.11).55 The regioselectivity can also be reversed by

suitably changing the substituents on the aryloxo ligand.56

22

/NMez
O 0 TI \NMez

 

 

cat
1 2 2 1 NR2
R : H + R-NHZ = R—( (1.11)
up to to 99% yield Me

Ackennann showed another user-friendly protocol for intermolecular hydroamination

of alkynes with various alkyl and arylamines using commercially available TiCl4.

Addition of tert—butylamine to TiCl4 generated the active catalyst in situ. This catalyst

tolerates various halides, which enables the synthesis of various indoles via one-pot

 

 

. . . . . 57.58
hydroamination/Heck coupling reaction sequence (Equation 1.12).
1) 10% TiCI4

1.2 equiv. ButNHz Ph

C' toluene, 105 °C, 20 h \

+ Et : Ph e Et (1 12)

NH2 2) 5% Pd(OAc)2 u '
5% NHC-HCI
KOBut

toluene, 105 °C, 20 h

Pri Fri —_|
, .. G)

Pr Pr'

23

Another class of the intermolecular hydroaminations of internal and terminal alkynes
with primary amines was developed by the Schafer group using amidate ligands (yields

as high as 97%). However, the enhanced reactivity also reduced the selectivity for some

45,59

terminal alkynes. -6] This methodology was further extended to the synthesis of 01-

amino acids and a-amino esters (Scheme 1.11).62

24

 

Scheme 1.11 Synthesis of a-amino esters via a hydroamination pathway

 

2 H2NAPh

a) catalyst ms. A

 

o N Ph
C H .65 C, 1211
6 6 > Burk/kc“.
b) TMSCN (1 equiv)

TFAA (2.5 equiv)
5 min

1.6.3 Research in the Odom group

The first example of non-Cp—based titanium catalyst, T1(NMe2)4, for alkyne

hydroamination was reported from our group in 2001.63 Hydroaminations of terminal

and internal alkynes were carried out with aniline and different aromatic amines. This

precatalyst is selective for Markovnikov products, as opposed to the szTiMez system

which produces anti-Markovnikov products selectively. The reactions were carried out
with 10% catalyst loading at 75 °C. The reactions with terminal alkynes were faster than
the internal ones. However, alkyne oligomerization and polymerization were observed
with phenylacetylene, hence low yield of the imine product was obtained. Unfortunately,

hydroamination reactions of alkynes with alkyl amines were not successful with this

precatalyst.

25

In search for a better catalytic system, a pyrrolyl-based ligand was used. Pyrrolyl

ligands are less it-donating to the metal due to its competition with the aromatic

stabilization of pyrrole (aromatic stabilization energy of pyrrole is ~21 kcal mol-l).64

This makes the metal center more Lewis acidic. A pyrrolyl-based ligand, szpma (dpma

= di(pyrrolyl-a-methyl)methylamine), was synthesized by Mannich reaction of pyrrole,

formaldehyde, and methylamine hydrochloride (88% yield). A new precatalyst,

Ti(dpma)(NMe2)2, was synthesized (Scheme 1.12) and applied successfully to

. . . 65-67 . .
intermolecular hydroamination of alkynes. Both terminal and internal alkynes were

hydroaminated by aliphatic and aromatic amines. The reaction of terminal alkynes with
aniline was most effective. A large number of functional groups (m-, p-OMe, halogen) on
aniline were tolerated. Although steric effects on the aniline were not dominant, a large

electronic effect was observed. In addition, the reactions were successfiil with alkyl
amines (cyclohexyl, benzyl, and benzhydrylamine). Compared to Ti(NMe2)4, this
catalyst was more selective towards Markovnikov products for most of the alkynes
(except l-phenylpropyne) (50:1 versus 3:1 for the reaction of l-hexyne with aniline).

This was attributed to the presence of the pyrrolyl ligand in the active species during

catalysis.

26

Scheme 1.12 Synthesis of Ti(dpma)(NMe2)2

H
2 o

+

H H , \ NMe2
o EtOH/HZO Wig/D T1(NMe2)4 \NTIi NMe2
> / _
2 H/U\H 55°C, 411 \ Me Ether / N l

88‘V / "N.
o H2dpma 92% Me

\

 

 

MeNHz-HCI
Ti(dpma)(NM92)2

The proposed mechanistic pathway (Scheme 1.13) leading to the imine product is
very similar to that for hydroamination of alkynes by zirconocene established by
Bergman and co-workers. The first step is the formation of the imido complex, followed
by [2 + 2]-cycloaddition of the alkyne forming an azametallacyclobutene
intermediate.The metallacycle then undergoes protonolysis by amine to form the imine

product and regenerates the imido species.

Scheme 1.13 Proposed mechanistic pathway for hydroamination of alkyne

Ti(dpma)(NMe2)2

k 2 NHMe2

protonolysis [2+2] R‘l — R2
Ph\ R1
PhNH2 8 l _ .
[Ti] 2 [T1] = T1(dpma)
R

27

However, to decrease the steric strain and increase the Lewis acidity of the metal

center, a slightly different pyrrolyl ligand was used. The complex was Ti(dpm)(NMe2)2,

where szpm is 5,5-dimethyldipyrrolylmethane (Scheme 1.14).68 This was an improved

precatalyst for intermolecular hydroamination of both terminal and internal alkynes with

aliphatic and aromatic amines. In fact, this was actually an order of magnitude faster than

the previous precatalyst, Ti(dpma)(NMe2)2, as revealed by kinetic experiments. Several
other Ti(dpm)(NMe2)2-type catalysts have been synthesized more recently. This includes

the use of 2,9—diaryldipyrrolylmethane derivatives.69 These also have been found to be

active catalysts for intermolecular alkyne hydroamination.

Scheme 1.14 Synthesis of Ti(dpm)(NMez)2

H
l N
25 O H Me Me H
cat. TFA N N TilNMe2l4
+ e \ l l / =
E120

neat, 5 min.
)L 53% 53%
Me Me

 

 

 

Ti(dpm)(NMe2)2

TFA = CF3C02H

28

 

1.7 Concluding Remarks

A variety of metal complexes covering most of the periodic table have been used to
catalyze hydroamination of alkynes. Both inter— and intramolecular versions have been
explored widely. Earlier examples of hydroamination involved harsh conditions such as
high temperature and pressure, while new reactions are facile at or near room
temperature. Hydroamination also has been applied towards the synthesis of amines and

different heterocycles.

During the development of titanium-based precatalysts for hydroamination, a new
reaction was discovered that involves hydrazines in place of amines. This process is
formally known as hydrohydrazination. Details on hydrohydrazination and its synthetic

applications will be discussed in the next chapter.

Reactions involving metal-ligand multiple bonds in catalysis, e.g.,
hydrohydrazination, are the main focus of this thesis. Expansion of this new chemistry
towards multicomponent coupling reactions and synthesis of different transition metal

hydrazido complexes will be discussed in the subsequent chapters.

29

 

1.8

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

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33

CHAPTER 2

Hydrohydrazination of alkynes
with monosubstituted hydrazines

2.1 Introduction

Hydrohydrazination is the formal addition of a hydrazine to an unsaturated C—C bond
resulting in a hydrazone or substituted hydrazine, which is shown for alkynes in Equation

2.1. This reaction allows access to heterocyclic structures that act as the core of many
natural products and pharmaceuticals]-4 Metal-catalyzed hydrohydrazination of alkynes
is primarily known for Ti, Co, Mn, Pd, and Zn. The catalytic process for these metals will

be discussed here. This is followed by the discussion of our work on hydrohydrazination

of alkynes using monosubstituted hydrazines.

 

.1 i
R1 — R2+ RiN-NH —cat'—> NI, ‘R: + N5; ‘R4 (21)
— R4/ 2 R1J\/R Rle/R1
hydrazone

34

2.1.1 Hydrohydrazination with Titanium

The first example of titanium-catalyzed addition of 1,1-disubsituted hydrazines to

alkynes was reported by our group in 2002.5 In these reactions, hydrazones are generated,

and, if aryl-substituted hydrazines are used, Fischer indole cyclization results in isolation

of the corresponding N-substituted indoles (Scheme 2.1).

Scheme 2.1 Titanium-catalyzed hydrohydrazination of alkynes and synthesis of an N-
substituted indole

NMez

QN;T i ”(\NMez
H . , ° ‘
2N N Me 10/o ~1er Me
(5 0"“:
Me : Ph + N
toluene, 100 °C, 20 h p
Me/U\/ h

 

 

 

 

 

F" Me Me Me _
\ (1’) [3,3]-sigmatropic '1.
H2N N EN -- A rearrangement HN’
Me Me H Me)§
H Ph Ph Ph
— NH3
Me
\
N
Me \
Ph

35

For 1,1-disubstituted hydrazine substrates, a pyrrole-based ligand framework on
titanium was found to be effective. The originally reported design was Ti(dap)2(NMe2)2
(1), where dap = 2-(dimethylaminomethyl)pyrrole. In addition, a thiolate-based catalyst

was also found to be very active, Ti(SC6F5)2(NMe2)2(l\lHMe2).

In titanium-catalyzed hydrohydrazination, the reactions are believed to follow a

pathway similar to that discovered for hydroamination by Bergman and co-workers using
zirconocene as catalyst (Scheme 2.2).6'8 In the first step, a titanium hydrazido(2—)
complex is generated from the bis(dimethylamido) precatalyst losing two equivalents of
dimethylamine.9 The hydrazido(2—) then undergoes [2 + 2]-cycloaddition with an alkyne

forming an azatitanacyclobutene intermediate. Finally, the metallacycle undergoes

protonolysis with hydrazine to form product and regenerate the metal-ligand multiple

bond.

36

Scheme 2.2 Proposed mechanistic pathway for the hydrohydrazination reaction using
1 ,1 -disubstituted hydrazines

NMez
[Ti l—NMe2

R
/
HzN-N\ — 2 NHMe2
R

2 [T1] = Ti(dap)
R
H

N NMe2
Hdap = [)4

 

More recently, Beller and co-workers have used a Cp-based (Cp = cyclopentadiene)

titanium catalyst for a similar transformation. nS-CpgTi(n2-Me3SiCZSiMe3) has been

used as the precatalyst for hydrohydrazination of terminal alkynes with N-phenyl-N-

methyl hydrazine (Scheme 2.3).IO Typical reaction conditions involve 2.5—10 mol%

catalyst at 85—100 °C, and the reactions are complete in 24 h. Addition of ZnClz to the

resulting hydrazones affords substituted N—methylindoles in 52—90% yield (Scheme 2.3).
Except for phenylacetylene, high Markovnikov selectivity is observed for other terminal
alkynes and 2-methyl-3-alkylsubstituted indoles are obtained as products. In the case of
phenylacetylene, the ratio of the indole products is 4:1 (Markovnikov:anti-Markovnikov).

In case of 5-chloropent-1-yne, the hydrochloride salt of N—methyl-3-(2-aminomethyl-)-2—

37

methylindole is obtained, which on addition of NaOH affords N-methyl-3-(2-

aminoethyl)-2-methyl indole in high yield (Scheme 2.4).

Scheme 2.3 Cp-based titanium-catalyzed hydrohydrazination of alkynes and synthesis of
substituted N-methylindoles

 

 

SiMeg
_ 1 Ti 1 1’“ 1’“ 7
F: ca . ,N ,N
+ t, R +
Ph toluene, 100°C L Me/J\/ H R
H2N-N: Markovnikov anti-Markovnikov
Me
ZnC|2
—NH3
Me Me
N N
W“? + / ..
R R

Scheme 2.4 Cp-based titanium-catalyzed hydrohydrazination of alkynes and synthesis of
substituted N—methyltryptamines

1) cat. %T'%
CI/V\\\ SiMes Me Me

SWb3

 

 

toluene, 100 °C, 24 11 N NaOH N
+ ; / Me / Me
ph 2) 3 equiv. ZnCl2
HzN—N/ toluene, 100 °C, 24 h
‘Me 64% NHz-HCI NH2

38

In addition, Beller has reported alkoxide-based ligands for titanium-catalyzed

hydrohydrazination with 5-chloropent-1-yne to generate N—substituted tryptamines
(Scheme 2.5).11 Here, 2.5—5 mol% of bis(2,6-di-tert-butyl-4-methylphenoxo)-

bis(dimethylamide)titanium is used as catalyst, and the reactions are carried out at 80—
120 °C. The products are isolated in moderate to good yield. The steps involved in
forming the tryptamine products are hydrohydrazination followed by [3,3]-sigmatropic
rearrangement of the resulting hydrazone combined with the elimination of ammonia.
The final step involves the nucleophilic attack of ammonia to the chloroalkane to
generate the tryptamine derivatives. Both electron-donating and electron-withdrawing
' groups are tolerated on the hydrazine during this reaction. Note that the presence of the

aryloxo ligand is necessary for the high yield of the indole product since only low yield

was obtained using Ti(NMe2)4 as the precatalyst.

39

Scheme 2.5 Synthesis of tryptamine derivatives by aryloxo-based titanium catalyst

/NMez
+ _
Ti NH3 Cl
° 3
\

 

+ Me
3 toluene, 100°C, 24 h N. 1
R R
NH
N/ 2 NaOH
l1
R

 

R1 = Ph, Benzyl, CH3

R2 = H, F, 01, CH3, OCH3

R3: H, Cl

 

Beller and co-workers have also reported the hydrohydrazination of tert-

butyldimethylsiloxy-2-propyne with N—methyl-N-phenylhydrazine generating 3-siloxy-2-

. . 12 . . . . . . .
methyl indoles (Equation 2.2). The optimized conditions for this reaction involve the

use of 5% Ti(NEt2)4 and 10% 2,6-di-tert-butyl-4-methyl-phenol at 100 °C in the

presence of a slight excess of hydrazine. Zan is used for the Fisher indole cyclization

step. A range of different substituents are tolerated in the para position of the hydrazine.

Note that the yields are higher for N-methyl indoles compared to N-benzyl indoles.

Recently, they have presented a similar transformation generating different N—substituted

tryptophol derivatives.l3 TiCl4/ButNH2-catalyzed hydrohydrazination of alkyne with

40

1,1-disubstituted alkynes have also been reported and the final products are N-substituted

. . . . . . . . l4
indoles. Here, T1Cl4 1S suffic1ently LeWis ac1dic to Circumvent the use of ZnClz.

. t
///\0’S'M928” 1- Ti(NEt2)4, 2.6-di-tert-butyl-

. t
4-methylphenol S'MeZB”
toluene \
+ > Me (2.2)
2. ZnClz N
N ,NH2 toluene, 100 °C, 24 h Me

1
Me

 

2.1.2 Hydrohydrazination with Cobalt

A cobalt(IlI) catalyst with a Schiff-base ligand has been reported by Carreira for

olefin hydrohydrazination.15 Both cyclic and acyclic olefins including monosubstituted,

1,1- and 1,2-disubstituted, and trisubstituted olefins are used in the presence of 1—5%
catalyst at 23 °C for 2—8 h (Equation 2.3). The reaction is highly selective for
Markovnikov products (except for esters in the case of 1,2-dusubstituted olefins). A
large number of functional groups including bromides and ketones are tolerated.
However, only low yields are obtained for unactivated 1,2-disubstituted olefins (crotyl

alcohol and cyclohexene).

41

9
‘ Na®
>90
_ O
ales/Do
O I \ _

 

O N R3
t
1 COzBu O < RZDKL
R
WRG'. = / e H t
N N R (2.3)
R t 1 equ1v. PhSIH3 / N
3“ 02C ButOZC I
ethanol, 23 °C, 2—8 h H

The proposed mechanistic pathway involves a hydrido cobalt intermediate, which
undergoes chemoselective addition of olefin to afford an organocobalt species (Scheme

2.6). The metal alkyl then adds to the N=N bond of azodicarboxylates to generate a

cobalt—nitrogen species. The final step involves o—bond metathesis of PhSiH3, which

regenerates the cobalt-hydrido complex.

Scheme 2.6 Proposed mechanistic pathway for Co-catalyzed hydrohydrazination of

olefin
1 3
R R 3 t
_ 2R Bu 02C.
2) < R1R 11'
R H H N. t
COL" COZBU
R3 H siHZPh LnCo—H
q
R N
R1 N/ \COZBut 1R2R3
|
COzBut R H
N /
PhSiH3 R3 H CoLn OBut
R1 il/ ‘cozeu
COzBut

42

The same group later reported the synthesis and use of a neutral Co(III) catalyst

active for a similar transformation. The catalyst was synthesized in a two-step procedure

starting from Co(OAc)2-4H20 and reacting with salicylaldehyde and a,a-dimethyl

substituted amino acid (Equation 2.4).16

 

H 1) 1 equiv. L H
o H20. argon 0 1' .112 Me
+ Co(OAc)2-4H20 e "-00-“ M (24)
OH 2) 1 equiv. L -N’ C')_ X 9
ethanol, air, 23 °C Me 0
77% Me 0
M3<Me
L = H2N COZH L = solvent

This complex is very active for hydrohydrazination of alkenes with di-tert-
butylazodicarboxylate. At first, monosubstituted olefins containing different functional
groups were used. The products, substituted hydrazines, were isolated in good yields.

Next, vinyl-substituted heterocycles, as shown in Equation 2.5a, were functionalized.

43

L' ”2

Oh. I .“N Me
2.5% _N«C.°~(%4Me

 

0..
ICOzBut Mine 0 0 Butozc.N,NHcozeut
Ar/_ + t /N=N . . f )\ (2.5a)
Bu 02C 1 equ1v. PhSIH3 Ar Me
CH2C|2, ethanol, 23 °C, 4 h
60—98°/o

L'=solvent
Me
N N\ ‘1, H N\ 1‘1.
127“: C2 1:71 [NH U OCH [,1
14’

The scope of the reaction has been extended to di- and tri-substituted olefins, and a
strong activating and directing effect of the phenyl group is observed. The products are
di- and trisubstituted styrene derivatives with exclusive formation of the hydrazine
product at the benzylic position. The use of this catalyst has also been extended to the

reaction with dienes and enynes generating various substituted allylic and propargylic

hydrazines as products (Equation 2.5b).17 It is interesting to note that only the C=C bond

of the enyne and terminal olefinic bonds are selectively hydrohydrazinated in this

reaction.

44

L' H2

 

OMC \N Me
_Nr% .OVO Me
2-5% 1 H
t Me MHO . , ,
[cozau O 3” 02C N N COzBut
, I r \ + N=N A7 (2 5b)

/ , . ,.
ButOZC PhS'Ha ’/

ethanol, 23 °C

L' = solvent

2.1.3 Hydrohydrazination with Manganese

Carreira and co-workers have reported highly efficient hydrohydrazination of alkenes

with a manganese-based catalyst.18 Dipivaloylmethanato (dpm) complexes of both
Mn(II) and Mn(III) are effective for this transformation. However, since Mn(dpm)2 is

very air sensitive, the Mn(dpm)3 complex is preferentially used. The Mn(III) complex is

very active, and the reaction works even at 0 °C with 2% catalyst loading (Equation 2.6).
A wide range of substrates including 1,2- and 1,1-disubstituted alkenes, 01,B-unsaturated

esters, tetrasubstituted alkenes, homoallylic alcohols are used with this new manganese-

 

 

based catalyst.
O
1 4 2/.
R R 3
2> < 3 R2 R
R R 1 4
R R t
. = , (2.6)
t iPhSil—l3 ButOZC’N‘n 0°23”
lCOzBu Pr OH 0 ",0 2— 311
t N=N
Bu 02C

45

2.1.4 Hydrohydrazination with Palladium

Addition of hydrazine or hydroxylamine to a C=C bond in 1,3-dienes has been carried

out in the presence of 1% [{Pd(n3—allyl)Cl}2] and 2% xantphos by Haltwig and co-

workers. It generates branched allylation products in excellent yields (Equation 2.7).19

Various nucleophiles such as benzophenone hydrazone, fluorenone hydrazone, 1-
aminobenzotriazole, and phenylhydrazine are used as substrates to add to C=C bond in
1,3-diene to yield the corresponding products. Benzophenone hydrazine has also been

used to add to a C=C bond in catalytic amination of allylic esters.

1% [{Pd(n3-aIIyI)CI}2]

 

3 4
1 2 R R 2% Xantphos 2 1 R3 R4
R R NNH2 + / \ #- R R NHN \ (2.7)
5R6 CHZCIZ, 23 °C, 24 11 6
R 76—98% RSR
PPh2 PPh2
R1, R2 = P1120, PhH 0
R3, R4 = H, Me xantphos: O O
R5 R6 = H

2.1.5 Hydrohydrazination with Zinc

Very recently, Beller and co-workers reported intermolecular hydrohydrazination of

terminal alkynes catalyzed by zinc salts.20 In particular, both ZnClz and mom; (OTf

= 0802CF 3) have been used for such transformations. The reactions are carried out in

THF at 100 °C for 24 h, and indole products are obtained in good to excellent yields

46

(Scheme 2.7). Both N-protected and NH-indoles are obtained. However, only terminal
alkynes are employed. Different functional groups including free and protected alcohols,

esters, pthalimide-protected amines are tolerated on the alkyne. On the other hand,

functional groups such as p-Me, p-prl, p-But, p-Br, p-Cl, p-F, p-OMe are tolerated on the

phenylhydrazine. This appears to be an elegant approach for the synthesis of both N-
protected and NH-indoles in an environmentally benign way bypassing N-protection of

hydrazine and N-deprotection of indole in the final product.

Scheme 2.7 Synthesis of NH—indole by zinc salts

 

 

 

///\C5H11 3 equiv. ZnC|2 C5H11 051-111
4' : ________> e
THF,100°C,24h // NyN R,// N
| \ 5o-97% R é 1R
/ ,NH l- J .
R. / iii 2 arylhydrazone Indole
R

R = Me, H; R' = p-Me, o-Me, p-pr’, p-But, p—F, p-Cl, p-Br, p-OMe; OTf = OSOZCF3

The Beller group has also extended the above hydrohydrazination reaction towards
the synthesis of pyrazolines and pyrazoles.21 Reaction between 3-butynol and
phenylhydrazine affords N-phenylpyrazoline and N-phenylpyrazole derivatives in the

presence of Zn(OTf)2 as catalyst (Scheme 2.8). Different substituents including o-Me, p-

Me, p-Cl, o-Cl, p-Br, p-CN, p-tolylsulfonyl are tolerated on the phenylhydrazine. The
reaction between 3-butynol and phenylhydrazine generates pyrazoline first, which on

filrther oxidation by air in the presence of acetic acid results in the pyrazole product in

47

good to excellent yield. No difference is observed in the yield of the pyrazole product if
the reaction is carried out with the isolated pyrazoline or all in one pot.
Scheme 2.8 Synthesis of pyrazoline and pyrazole by Zn(OTf)2-catalyzed

hydrohydrazination

R_g NH 5% Zn(OTf)2 1
OH + / , >
é/V N 2 THF, 100 °C, 24 11

 

 

 

arylhydrazone

R+ R+
— H20 ’ CH3COOH ’

 

 

)NLN) air, 50 °C, 24-72 h 7 D
Me 52—99% Me

pyrazoline pyrazole
R = p-Me, o-Me, p-CI, p-Br, p-CN, tosyl %Tf =%SOZCF3

A further extension of this chemistry involves the synthesis of
dihydropyridazinones.22 Hydrohydrazination of 4-pentynoic acid with different
arylhydrazines generates aryl-substituted 4,5-dihydro-3(2H)-pyridazinones in the
presence of ZnClz (Scheme 2.9). This is a convenient method to form pyridazinones in

one-pot procedure and does not require any special handling of the reagents or air- or

moisture-free solvents and atmosphere.

48

Scheme 2.9 Synthesis of pyridazinones via hydrohydrazination using ZnClz

O

+

ON,NH2

H

3 equiv. ZnCl2

A

THF, 100 °C, 24 11 v

OH

-M 1
8N0

N

I1

NH

 

 

 

<3

arylhydrazone

49

Me
I
— H 0 Y1
2 a N N o
90% i
pyridazinone

2.2 Synthesis of NH-indoles

Since the discovery of the Fischer indole synthesis in 1883, synthesis and

. . . . . . 23 .
functionallzatlon of lndoles continued to be an active area of research. A variety of

modern and well-documented methods are also available for NH—indole synthesis.24 For

example, Pd-catalyzed coupling and annulation reactions have been employed in the

. . 25-34 . . . .
syntheSls of indole frameworks. Recently, titanium-based hydroammatlon of

alkynes followed by Heck couplings have been developed by Ackermann for the

synthesis of NH—indoles (Equation 2.8).35

1) 10% TiC|4

1.2 equiv. ButNHz Ph

0' toluene, 105 °c, 20 11
+ Et : Ph 47 \ Et (2 8)
NH2 2) 5% Pd(OAc)2 fl
5% NHC-HCI
KOBut

toluene, 105 °C, 20 h

Pr, Pr, |
. = e
where NHC HCI QN¢\N© Cl
' ~_—’ -

 

 

50

2.3 Aim of the current project

We have seen that titanium-catalyzed hydrohydrazination of alkynes with 1,1-
disubstituted hydrazines forms the corresponding hydrazones. If one of the substituents is

an aryl or phenyl group, the hydrazones can be converted to N-substituted indoles in the

presence of an external Lewis acid, ZnC12 (Scheme 2.1). However, indoles present in

. . . . 36-39
natural products and pharmaceuticals more often contam the NH-functlonallty.

Our interest here is to carry out direct synthesis of NH-indoles using

hydrohydrazination. For this we have developed a new pyrrole-based ligand for the

hydrohydrazination of alkynes using monosubstituted hydrazines.40 This is the first

titanium-based catalyst active for monosubstituted hydrazines. In addition, this is the only
reported catalyst that is active for both terminal and internal alkynes. NH—hydrazones are
generated in situ by the catalytic process, and a variety of heterocycles are synthesized
using this methodology. The development of this new precatalyst, its substrate scope, and
applications to various heterocyclic synthesis will be described in the following sections.
This project was carried out with the help of Dr. Eyal Barnea who joined our group as a
post-doctoral associate during the exploration of this new methodology. Also note that
during the course of our work, the Beller group developed a zinc-catalyzed
hydrohydrazination to synthesize NH-indoles using exclusively terminal alkynes. This

work was described in Section 2.1.5.

51

2.4 Results and Discussion

In an attempt to extend the hydrohydrazination reaction to monosubstituted

hydrazines, we investigated the reaction between l-hexyne and phenylhydrazine with our

previous catalysts Ti(dap)2(NMe2)2 (l) and Ti(SC6F5)2(NMe2)2(NHMe2) at 100 °C for

16 h. However, no hydrohydrazination product was observed. With Ti(NMe2)4, where all

the ligands are protolytically labile, we did not observe any hydrazone product. Reaction
of l with 10 equiv of phenylhydrazine resulted in greater than l equivalent of Hdap being
generated per titanium. As a consequence, the clap ancillaries were assumed to be too

protolytically labile to support monosubstituted hydrazine reactivity.

Therefore, we attempted to increase the protolytic stability of the ancillary ligand set

by using a tetradentate ligand instead of two bidentate ligands. For the synthesis of the

new tetradentate ligand (Scheme 2.10), Hdap“.43 was converted to N-(Boc)-dap (2) with

(Boc)20 and DMAP (where, 800 = terI-butyloxycarbonyl, DMAP = N,N-

dimethylaminopyridine). The tertiary amine of the lBoc-protected dap was quarternized

with methyl iodide to form the corresponding ammonium salt (3). Reaction of 3 with

N,N'-dimethyl-1,2-ethylenediamine in the presence of excess K2C03 formed the desired

ligand Hzenp (where, Hzenp = N,N-bis(a-methylpyrrol)-N,N-dimethylethane-1,2-

diamine) (4) in ~50% yield with concomitant pyrrole nitrogen deprotection.

52

The X-ray crystal structure of 4 is shown in Figure 2.1. There is intermolecular

hydrogen bonding between the hydrogen atom of pyrrole nitrogen and the tertiary amine

nitrogen.

Scheme 2.10 Synthesis of Hzenp (4)

(800)20 (1 equiv.)

 

 

H We DMAP (0.15 equiv.)
2 M CH2C|2, RT, 18h
Hdap 55%
Me-N N—Me
M NH HN M
’— / NH e e

CH3CN, 105 °c, 2 d
50%

BOC

I

N NMez
2 M
2

Mel (2.2 equiv.)
THF, RT, 18 h

87%

 

P09 <9 e
NMe3|

2E>—/

3

Figure 2.1 ORTEP representation (50% probability level) of Hzenp (4).

 

Next, a new titanium precatalyst Ti(enp)(NMe2)2 (5) was prepared by reaction of one
equivalent of Hzenp with Ti(NMe2)4 as shown in Figure 2.2. The expected structure has
two pyrroles coordinating in an nl-fashion with two dimethylamido fiagments mutually

. . . . . . 44
cis, Wthh lS conSlstent With the spectroscoplc properties of the molecule.

Figure 2.2 Synthesis of Ti(enp)(NMe2)2 (5) and comparison with Ti(dap)2(NMe2)2 (1).

Me-N N-Me —~ NMe2
Ti(NMezl4 + 7‘ ""‘T1"““e2
\ NH / 870/0 Me/ |\/N\/|Q

Ti(eanNMezlz (5)

 

H2enp

NMez

"”133
MGZN

Ti(dap)2(NM62)2 (1)

Previous catalyst

In order to probe the substrate scope of Ti(enp)(NMe2)2 (5), both terminal and

internal alkynes were treated with different monosubstituted hydrazines in the presence
of catalytic 5. Test reactions using 1-hexyne and phenylhydrazine with 10 mol% catalyst

loading at room temperature proceeded to near full conversion, but the reaction rates

54

were impractically slow requiring ~ 5 days to reach completion. The reaction of l-hexyne
with phenylhydrazine was optimized to run at 80 °C with 5 mol% 5 and was complete in
2 h. Under the optimized conditions, reactions were carried out with 5 mol% 5 in toluene
at 80 °C for 4.5—41 h (Table 2.1). Hydrazones of l-hexyne were also obtained with
methyl- and benzylhydrazine. Only the Markovnikov product was observed in these cases

(Equations 2.9 and 2.10).

In order to apply this methodology towards indole synthesis, arylhydrazines were
reacted with different alkynes. In large part for expediency of product isolation and

characterization, arylhydrazones (observed by GC/F ID and GCMS) were converted to

indoles in a one-pot procedure with excess ZnClz. In all cases, the hydrazones were

cleanly generated and observed prior to ZnC12 addition. Therefore, this methodology is in

general applicable to hydrazone synthesis.

 

 

 

 

lllle
n 5% T1(enp)(NMe2)2 N‘" NH
H : Bu + MeaN,NH2 o T /U\ n (2.9)
H toluene, 80 C, 16h Me Bu
73%
5
. NH
H _ B n (DAN/””2 5%T1(enp)(NM92)2 N” 210
_ u + F '
toluene, 80 °C, 16“ Me/1L Bun ( )
60%
7

55

The regioselectivity of the products was dependent on the electronic and steric
properties of the alkyne. Only the Markovnikov product was obtained for reaction of 1-
hexyne with phenylhydrazine (Entry 1, Table 2.1). For 2-hexyne (Entry 2, Table 2.1), the
apparent hydrohydrazination regioselectivity, based on the ratios of isolated indoles, is
1:4 with a preference for hydrazine addition to the 3-carbon (Scheme 2.11). If the two
alkyl groups (methyl and n-propyl) in this alkyne are considered electronically
equivalent, this reaction demonstrates the preference of the catalyst to create the new C—

N bond at the more hindered carbon in the triple bond.

Scheme 2.11 Reaction of Z-hexyne with phenylhydrazine catalyzed by 5

 

 

 

 

Me : Prn N frN(H)Ph N J.,N(H)Ph
5% Ti(enp)2(NMez)2 /u\ A n
+ > n +
toluene, 80 °C, 16 h Me BU Et Pr
Ph\N,NH2 80%
H l l l 1 I 3.9 l 1
Me Et
HN HN
\ \
3 9
4.
Fr"
HN \
1 : 1.3 : 2.6 Me
10

56

For symmetrical 3-hexyne, a 1:25 mixture of indole products are obtained due to a

lack of selectivity in the Fischer indole cyclization (Entry 3, Table 2.1).

For aryl-substituted alkynes, there is an electronic preference for generating the new
C—N bond [3 to the phenyl group. Consequently, for phenylacetylene there is a steric
preference for addition a to the phenyl group and an electronic preference [3 to the phenyl
group. This leads to a mixture of products for this substrate (Entry 6, Table 2.1), and the
hydrohydrazination reaction with phenylhydrazine resulted in a 122.6 mixture favoring
the electronically preferred indole from anti-Markovnikov addition. Adding even a small
amount of sterics to the terminal carbon lessens the steric preference, and for the 1-
phenylpropyne reaction, only the indole product from electronically preferred B-addition

of hydrazine with respect to the phenyl group was observed (Entry 4, Table 2.1).

Protected alcohols and amines on the alkyne were employed to provide TBS-
protected (where TBS = tert-butyldimethylsilyl) 2-methyltryptophol and 2-methyl-N, N-
diethyltryptamine, respectively, after the Fischer indole cyclization (Entries 7 and 8,

Table 2.1).

57

Table 2.1 Hydrohydrazination of alkynes with phenylhydrazine

 

 

 

 

 

 

 

 

 

 

 

 

, Fl’h F1)“ _

1 _ 2 . NH HN, H

R — R 5% T1(enp)2(NMe2)2 N“ N 2 3-5 ZnC|2 N R3
+ —> 2+ ;

Ph NH2 toluene, 80°C,4.5—41h R1J\/R Rl’lK/R 100—120°c, /
1N! 16—24h R4
H L 2

observed by GC/F ID and GCMS
Ratio Yleld
Entry Substrate Product(s) (azb or azbzc) (%)a
Me
HN \
l H : Bu" Pr" — 87
8
Me
HN
&\Prn
8
Et
HN \
2 Me : P1" Et 1:1.3:2.6 80
9
Pr”
HN
\
61m
10
Et
HN
\
CR3
3 Et — Et 9 125 76
_ Prn ' '
HN
[9Me
10

 

58

Table 2.1 (Cont’d.)

 

 

 

 

 

 

 

 

Me
HN \
4 Me : Ph Ph — 7O
11
Ph
HN \
5 Ph : Ph Ph — 55
12
Ph
HN \
6 H : Ph 13 1:26 70
HN \
(9%
14
Me
’MeM HN \
_ ./ e
7 O SKB t b — 62
__ ” OTBS
H _
15
Me
NEt2 HN \
8 — 48
H : NEt2
16

 

a
Reaction time for the first step: 16 h for entries 2-4 and 7; 4.5 h for entries I and 6; 4] h for entry 5,

b
24 h for entry 8. TBS = tert-butyldimethylsilyl

The effect of using coordinating solvents instead of toluene was also studied. It was
found that using THF or acetonitrile as the solvent had no obvious effect on the
hydrohydrazination reactions. In addition, these solvent changes had no obvious effect on

the indole cyclization for hydrazone derived from 1-hexyne and phenylhydrazine.

To determine the sensitivity of the titanium catalysis to a variety of potential amine
bases, we ran the reaction between l-hexyne and phenylhydrazine in the presence of
several amines. It was observed that there was no significant effect for addition of
quiniclidine, triethylamine, 2,6-lutidine, or pyridine. The conversions after 18 h at 80 °C
with 10 mol% 5 and 20 mol% base were approximately the same (66—71%) as in the

absence of these bases (75%).

From the reaction of 5-chloropent-1-yne with phenylhydrazine two products were
obtained (Scheme 2.12). One product, 3-methyl-l-phenyl-1,4,5,6-tetrahydropyridazine
(17), was obtained by hydrohydrazination followed by intramolecular elimination of
hydrochloric acid and cyclization in situ. The remaining hydrazone 19 undergoes Fisher
cyclization, perhaps catalyzed by HCI in the reaction mixture, generating the salt of 2-
methyltryptamine (18). Free 2-methyltryptamine (20) was obtained on basification.

Compound 17 was found to be very stable in the presence of HCI generated in the

. . . . . . . 45
reaction mixture, and also external LeWis ac1d as observed prev10usly in the literature.

46 The products were obtained in a 1:1 ratio, in an overall yield of 64%.

Addition of 1.1 equivalents of triethylamine to a similar reaction between 5-

chloropent-l-yne and phenylhydrazine resulted in the formation of two compounds, 17

60

and 19, which were observable by GCMS. Sequential addition of ZnC12 and NaOH

provided 2-methyltryptamine 20 (Scheme 2.12).

Scheme 2.12 Hydrohydrazination of 5-chloropent—1-yne with phenylhydrazine

H A
“—\ 5% T1(enp)(NMe2)2 (5) ,N / Me
+ Cl R +
toluene, 80 °C, 16 h l)
Me (+) e

64%
Q 17 a "“3“
’NH2 1:1

11

10% Ti(enp)(NMe2)2

1.1 NEt3
toluene, 80 °C, 16 h

—+J’N© 1) 3 ZnCI2
toluene, 100 °C, 18 h M
N > + e
TUMM 2) NaOH b /
62% Me

17 20

NaOH

 

 

 

NH2

 

observed in GC/FID and GCMS 1:1

Substituted phenylhydrazines were also used in reactions with l-hexyne, and the
products were isolated in good yield. Corresponding indoles were obtained when p-Me,
p-F, and p-OMe substituted phenylhydrazines were used. Only the products derived from

Markovnikov addition to the alkyne were obtained in all of these cases (Table 2.2).

61

Table 2.2 Hydrohydrazination with substituted phenylhydrazines

X

H
H : Bun _ N
5% T1(enp)2(NMez)2 NH 3 ZnC|2 / Me
+ > 5" =
toluene, 80 °C, 16 11 j: 100 °c, 16 11 x Prn
x Me Bu”
0 ,NH2

 

 

 

 

 

 

 

N
H
Entry X Product Yield (%)
H
N
Me
1 Me “new 64
n
Pr
21
H
N
Me
2 F FW 70
Fr"
22
H
N
/ Me
3 OMe mom 76
Pr

23

 

62

The scope of the reaction was also extended to diynes. When nona-l,4-diyne was
reacted with phenylhydrazine at 80 °C for 16 h, it led to the formation of substituted
dihydropyridazine (24) in one step along with a substituted pyrazole product (25) (Entiy
1, Table 2.3). In this particular case, the dihydropyridazine (24) was obtained as the
minor product (24:25 = 1:26). The hydrazone generated was due to exclusive addition of
the phenylhydrazine in a Markovnikov fashion to the terminal triple bond. The formation
of the observed products can be explained as shown in Scheme 2.13. We speculate that
cyclizations may occur through an allene intermediate under the reaction conditions,

which can then undergo either 6-endo or S-exo trig cyclization, giving rise to 24 or 25

respectively.47’48 An alternative 1,2-insertion pathway involving the alkyne and a
titanium hydrazido(1—) of the initial hydrohydrazination product cannot be ruled out

. . . 49-53,54
under these reaction conditions.

When octa-l,7-diyne was reacted with 2.2 equivalents of phenylhydrazine at 100 °C

for 24 h, hydrohydrazination at both the triple bonds results. Fischer indole cyclization in
one pot furnished l,2-bis(2-methyl-1H—indol-3-yl)ethane55 (26) in 70% yield (Entry 2,

Table 2.3).

63

Scheme 2.13 Possible pathways to 24 and 25

 

 

 

 

 

 

H
\\ / Bun Q
/ 0 .
+ ”TKenprMem e N,N Bu” + N,N Bu”
Toluene, 812 °C, 16 11 M M
P11NHNH2 59 /° Me 125 Me
24 25
NH ,NH H
Nr..\ H N L A n
n C J Bu
C‘é Bu
Me
H H
V
6-endo trig 5'9“ tr ’9
T _ 1—
NH NH
N' / Bu" ~ ‘ N“ i n
/
MGM Me/IKFC BU
_. J H

 

 

allene intermediate

64

Table 2.3 Hydrohydrazination with diynes and enyne

 

.. a Isolated
Entry Substrate Condltlons Pmd‘mt Yield (%)

Q, Q
l l A NN b
l -penty|
¢ 11. / MJ3);

24

 

 

26
Me N
é " 11
3 c 52
27

 

0A is 5 mol% 5 at 80 °C for 16 h, B is 5 mol% 5 at 100 °C for 24 h followed by 4 equiv ZnClz at 100

b
°C for 24 h, C is 5 mol% 5 at 80 °C for 24 h followed by 3 equiv ZnClz at 100 °C for 36 h. 24:25 =
1:2.6.

One enyne substrate was examined with phenylhydrazine, l-ethynylcyclohex-l-ene

(Entry 3, Table 2.3). After the formation of the hydrazone, which was not isolated,

addition of ZnClz resulted in Michael addition of the B-nitrogen of the hydrazone across

the C=C bond of the cyclohexenyl moiety to yield the substituted indazole56’57 27 in

52% yield.

65

2.5 Concluding Remarks

A new catalytic hydrohydrazination reaction of monosubstituted hydrazines with
alkynes has been developed. This was accomplished by suitably designing the ligand
framework on the titanium center. Both terminal and internal alkynes have been used
with aliphatic as well as aromatic hydrazines. The regioselectivity of the addition is
highly dependent on the electronic and steric nature of the alkyne, and the catalyst is
applicable to generating both N-alkyl- and N-arylhydrazones. This methodology has also
been applied to the synthesis of different NH-indoles including 2-methyltryptamine and
tryptophol derivatives, which are important building blocks of different natural products.
As discussed here, many different 5- and 6-membered heterocycles are available using

titanium-catalyzed hydrohydrazination.

66

2.6 Experimental
General Considerations

All manipulations of air sensitive compounds were carried out in an MBraun drybox
under a purified nitrogen atmosphere. Pentane (Spectrum Chemical Mfg. Corp.), toluene
(Spectrum Chemical Mfg. Corp.), ether (Columbus Chemical Industries Inc.),
dichloromethane (EM Science), acetonitrile (Spectrum Chemical), and tetrahydrofuran
(JADE Scientific) were sparged with nitrogen to remove oxygen then dried by passing
through activated alumina. Hydrazines were purchased from Aldrich Chemical Company
and dried by distillation from KOH under dry nitrogen. Alkynes were distilled from CaO

under dry nitrogen. Octa—1,7-diyne was purchased from GFS chemicals, and distilled

over CaO under dry nitrogen. Nona-1,4-diyne,58 and l-ethynylcyclohex-l-enes9 were

prepared according to the literature procedures. (BOC)2O (BOC = t-butyloxycarbonyl)

and DMAP (4-dimethylaminopyridine) were purchased from Aldrich and used as

received. Ti(NMez)460 was prepared using the literature procedure. The Hdap (where dap
= 2-(dimethylaminomethyl)pyrrole) ligand was prepared as described in the literature.22
Deuterated solvents were dried over purple sodium benzophenone ketyl (C6D6) or
phosphoric anhydride (CDC13) and distilled under nitrogen. 1H and 13C spectra were
recorded on Inova-3OO or VXR-SOO spectrometers. IH and 13C assignments were
. . . l 1 l3 1
confirmed when necessary With the use of two-dimenSlonal H— H and C— H

. . . . . 13
correlation NMR experiments. Routine coupling constants in C NMR are not reported.

67

All spectra were referenced internally to residual protiosolvent (1H) or solvent (13C)

resonances. Chemical shifts are quoted in ppm, and coupling constants in Hz.

68

Synthesis of butyl-2-((dimethylamino)methyl)-lH-pyrrole-l-carboxylate (2)

Elm

A 500 mL round bottom flask was charged with Hdap (2.617 g, 21.10 mmol),

M62

(80079 (4.600 g, 21.10 mmol), and DMAP (0.386 g, 3.1 mmol) in dichloromethane

(250 mL) and was allowed to stir at room temperature overnight. The solution was

quenched with water (20 mL) and extracted with ether (3 X 20 mL). Combined organic

layers were washed with water. The organic layer was then dried over MgSO4, filtered,

and volatiles were removed under vacuum. The product was isolated by distillation under

vacuum (~65 °C, 0.1 Torr) as a colorless oil in 66% yield (3.120 g, 13.90 mmol). 1H
NMR (499.7 MHz, CDC13): 7.18 (dd, 1 H, JHH = 1.8, 3.4 Hz, 5H—pyrrole), 6.11 (m, 1 H,
4H—pyrrole), 6.08 (t, JHH = 3.3 Hz, 1 H, 3H—pyrrole), 3.65 (s, 2 H, CH2), 2.26 (s, 6 H,

NCH3), 1.57 (s, 9 11, CCH3). '3C1'H} NMR (125.7 MHz, CDCl3): 149.9, 132.7, 121.5,

113.3, 109.7, 83.3, 56.6, 45.5, 28.0. Elemental Analysis; Experimental (Calc.), C: 63.88

(64.26). H: 8.98 (8.99). N: 13.11 (12.49). MS (EI) m/z = 224 (M+).

69

Synthesis of [N-(t-butoxycarbonyl)-2-(trimethylaminomethyl)pyrrole]I (3)
H3C CH
0 71/033
yo
we
/ @N

To a 500 mL round bottom flask was added 2 (9.870 g, 44.00 mmol), methyliodide

C)
Me3 I

(6.870 g, 48.40 mmol), and THF (250 mL). The reaction was allowed to stir at room
temperature overnight. A white precipitate appeared during the reaction. The precipitate

was filtered, washed with THF, and dried under vacuum to yield the product as a white

powder in 87% yield (14.00 g, 38.00 mmol). 1H NMR (499.7 MHz, CDC13): 7.35 (d,
JHH = 3.4 Hz, 1 H, 5H-pyrrole), 6.85 (dd, JHH = 1.7, 3.6 Hz, 1 H, 4H-pyrrole), 6.27 (t,
JHH = 3.4 Hz, 1 H, 3H—pyrrole), 5.22 (s, 2 H, CH2), 3.37 (s, 9 H, NCH3), 1.58 (s, 9 H,

CCH3). 13C{'H} NMR (125.7 MHz, CDCl3): 149.4, 125.5, 123.3, 120.9, 111.4, 86.0,

61.4, 52.8, 27.9. Elemental Analysis; Experimental (Calc.), C: 42.81 (42.63). H: 6.52

(6.33). N: 7.75 (7.65). mp 180 °C ((160).

70

Synthesis of Hzenp (4)

Me-N N-Me
——— / NH
\ NH /
A round bottom flask (500 mL) was charged with K2CO3 (7.561 g, 54.80 mmol) in

dry acetonitrile (250 mL) and N,N’-dimethylethy1enediarnine (0.483 g, 5.50 mmol). To
the flask was added 3 (4.091 g, 10.90 mmol). Initially, the reaction was a light brown
colored suspension and was refluxed at 105 °C for 2 d. After that, the suspension was
allowed to cool to room temperature and sit, producing a brown solution with white
precipitate. The mixture was filtered, and the filtrate was dried by rotary evaporation.
Ethylacetate was added to the brown oily product, which led to additional white
precipitate. The brown solution was filtered, and the filtrate was dried under vacuum. The
dark brown resulting oil was subjected to column chromatography on alumina using 60%
ethylacetatezpentane followed by 10% MeOHzethylacetate. The product was isolated as a
pale yellow solid in 50% yield (0.670 g, 2.70 mmol). X-ray quality crystals were grown

at room temperature from dichloromethane solution of 4 with one drop of toluene by

slow evaporation. 1H NMR (499.7 MHz, 00013): 9.38 (b, 2 H, NH), 6.69 (q, JHH = 2.4
Hz, 2 H, 5H—pyrrole), 6.12 (q, JHH = 2.7 Hz, 2 H, 4H—pyrrole), 5.99 (m, 2 H, 3H-
pyrrole), 3.58 (s, 4 H, CHz-pyrrole), 2.48 (s, 4 H, CHZCHZ), 2.22 (s, 6 H, CH3). I3C{1H}

NMR (125.7 MHz, CDCl3): 128.9, 117.4, 108.0, 107.0, 54.8, 54.1, 42.8. m.p.: 95-97 °C.

71

Synthesis of Ti(enp)(NMe2)2 (5)

All the manipulations were carried out inside an inert atmosphere glove box. A filter

flask (125 mL) was loaded with Ti(NMeZ)4 (0.388 g, 1.70 mmol) in ether (2 mL) and

cooled inside the cold well. To the solution was added cold 4 (0.427 g, 1.70 mmol) in
ether (25 mL) dropwise over a period of 15 min. The reaction was allowed to warm to
room temperature and stir overnight producing a dark red solution. Volatiles were

removed in vacuo. The product was recystallized from 1:1 etherzpentane as an orange

solid in 87% yield (0.560 g, 1.50 mmol). 1H NMR (499.7 MHz, CDC13): 6.98-7.02 (m, 2
H, SH-pyrrole), 6.10 (app t, JHH = 2.3 Hz, 2 H, 4H—pyrrole), 5.80—5.84 (m, 2 H, 3H-
pyrrole), 4.50 (d, JHH= 15.4 Hz, 2 H, CHH-pyrrole), 3.67 (d, JHH = 15.3 Hz, 2 H, CHH-
pyrrole), 3.38 (s, 12 H, N(CH3)2), 2.55 (d, JHH= 9.2 Hz, 2 H, CHH-CHH), 2.14 (d, JHH
= 8.8 Hz, 2 H, CHH-CHH), 1.96 (s, 6 H, CHZNCH3). I3C(‘H1 NMR (75.4 MHz,

CDCl3): 138.4, 126.0, 107.0, 99.8, 62.3, 62.1, 49.1, 47.6. mp. 126-128 °C. Complex 5

after many attempts did not pass elemental analysis. Spectra for the complex are included

in the supporting information.

72

Synthesis of the E—benzylhydrazone of 2-hexanone (7)

Q

NH

3"

N

)L n

Me Bu
Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.057 g, 0.15 mmol) in toluene (750 11L), benzylhydrazine (300 11L, 3.00 mmol), and 1-
hexyne (350 11L, 3.00 mmol). The reaction vessel was sealed and removed from the dry
box to be heated at 80 °C for 16 h. The solution was then cooled to room temperature,
diluted with ether, and passed through a pad of alumina in a fritted funnel. Volatiles were
removed from the filtrate under vacuum. The resulting dark brown oil was subjected to

column chromatography on alumina using 4:1 hexanes:ethylacetate as eluent. The

product was isolated as brown oil in 60% (0.360 g, 1.80 rmnol). 1H NMR (499.7 MHz,
CDC13): 7.34 (m, 2 H, 0-H Ph), 7.31 (d, 2 H, m-H Ph), 7.26 (t, 1 H, JHH= 7.1 Hz, p-H
Ph), 1.36-1.23 (br s, 1 H, NH), 4.34 (s, 2 H, NH-CHzPh), 2.21 (t, 2 H, JHH: 8.2 Hz,
C(=N)CH2), 1.69 (s, 3 H, C(=N)CH3), 1.52-1.40 (m, 2 H, JHH = 7.9 Hz,
C(=N)CH2CH2), 1.36-1.22 (m, 2 H, JHH= 8.0 Hz, CH3CH2), 0.98 (t, 3 H, JHHZ 7.5 Hz,
CHZCH3). l3C{1H} NMR (125.7 MHz, CDC13): 149.7, 139.6, 128.4, 128.3, 127.1, 55.4,

38.8, 29.1, 22.4, 14.3, 13.9. MS (EI) m/z = 204 (M+).

73

Synthesis of 2-methyl-3-propyl-lH-indole (8)

Me

HN
\
Pr"

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.114 g, 0.30 mmol) in toluene (1.5 mL), phenylhydrazine (295 11L, 3.00 mmol), and 1-
hexyne (350 uL, 3.00 mmol). The tube was sealed and removed from the dry box for

heating at 80 °C for 4.5 h. The reaction was then allowed to cool to room temperature,

taken inside the box, and excess ZnC12 (1.227 g, 9.00 mmol) was added. It was heated at

100 °C for 24 h. After that, the reaction was allowed to cool to room temperature, diluted
with ether, and passed through a pad of silica in a fritted funnel. Volatiles were removed

from the filtrate in vacuo. The resulting dark brown oil was subjected to column

chromatography on silica gel with 7:3 dichloromethanezpentane as eluent. The product“
was isolated as pale yellow oil in 87% yield (0.450 g, 2.60 mmol). 1H NMR (299.8 MHz,
CDC13): 7.65 (br s, 1 H, NH), 7.48 (d, 1 H, JHH = 7.5 Hz, 4H—indole), 7.24 (dd, 1 H, JHH
= 3.5, 6.2 Hz, 7H—indole), 7.12 — 7.02 (m, 2 H, 5H— and 6H-indole), 2.66 (t, 2 H, JHH =
7.5 Hz, CH3CH2CH2), 2.53 (s, 3 H, 2-CH3), 1.63 (m, 2 H, CH3CH2CH2), 0.93 (t, 3 H,

JHH = 7.3 Hz, CH3CH2). I3C{1H} NMR (75.4 MHz, CDC13): 135.3, 130.7, 128.9,

120.7, 118.9, 118.2, 112.3, 110.0, 26.2, 23.8, 14.1, 11.7. Elemental analysis;

74

Experimental (Calc.), C: 83.17 (83.19). H: 8.88 (8.73). N: 8.05 (8.08). MS (EI) m/z = 173

(M+).

75

Synthesis of 2-phenylindole (13) and 3-phenylindole (14)

Ph
HN HN
5; ‘Ph : \>‘Ph

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5

(0.093 g, 0.25 mmol) in toluene (1.2 mL), phenylhydrazine (518 11L, 4.90 mmol), and
phenylacetylene (538 11L, 4.90 mmol). The tube was sealed and removed from the dry

box for heating at 80 °C for 4.5 h. The reaction was then allowed to cool to room

temperature, taken inside the box, and excess ZnC12 (3.279 g, 24.50 mmol) was added.

The tube then was heated at 120 0C for 24 h. After that, the mixture was allowed to cool
to room temperature, diluted with ether, and passed through a pad of silica in a fritted
funnel. Volatiles were removed from the filtrate in vacuo. The resulting dark brown oil

was subjected to column chromatography on silica gel with 1:1 petroleum ether:ether as

eluent. The products62 were isolated as a pale yellow oil in 70% yield (0.660 g, 2.60

mmol). IH NMR (299.8 MHz, CDCl3): 8.40 (br s, 1 H, NH), 8.38 (br s, 1 H, NH), 7.95
(s, 1 H, 2-CH), 7.78-7.15 (m, 9 H, Ph), 7.38-7.18 (m, 9 H, Ph) 6.81 (s, 1 H, 3-CH).

l3C{'H} NMR (75.4 MHz, CDC1'3): 137.9, 136.8, 136.6, 135.5, 132.4, 129.3, 129.0-

125.1, 122.4-119.8, 118.4, 113.2, 111.4, 110.9. 100.0 (b). MS (EI) rn/z = 193 (M+).

76

Synthesis of 2-methyl-3-(2-(dimethyl(t-butyl)siloxy)ethyl)indoIe (15)

Me
HN
\

SiMezBut
Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.024 g, 0.07 mmol) in toluene (315 uL), phenylhydrazine (124 11L, 1.30 mmol), and

went-4-ynyloxy)t-butyldimethylsilane (0.250 g, 1.30 mmol). The tube was sealed and

removed from the dry box for heating at 80 °C for 16 h. The solution was then allowed to

cool to room temperature, taken inside the box, and excess ZnClz (0.506 g, 3.90 mmol)

was added. The reaction was heated at 100 °C for 16 h. The mixture was allowed to cool
to room temperature, diluted with ether, and passed through a pad of silica in a fitted
funnel. Volatiles were removed from the filtrate in vacuo. The resulting dark red oil was
subjected to column chromatography on silica gel with 7:3 hexaneszethylacetate as

eluent. The product was isolated as pale yellow oil in 62% yield (0.220 g, 0.80 mmol).

1H NMR (499.7 MHz, CDC13): 7.74 (br s, 1 H, NH), 7.52 (d, 1 H, JHH = 7.4 Hz, 7H-
indole), 7.28 (d, 1 H, JHH = 6.9 Hz, 4H-indole), 7.17 (m, 2 H, 5H- and 6H-indole), 3.65
(t, 2 H, JHH = 8.9 Hz, OCHz), 2.98 (t, 2 1H, JHH' = 7.4 Hz, OCH2CH2), 2.41 (s, 3 H, 2-

CH3), 0.86 (s, 9 H, CCH3), 0.11 (s, 6 H, SiCH3). '3C{'H} NMR (125.7 MHz, CDCl3):
135.2, 131.7, 128.9, 120.9, 119.1, 117.9, 110.1, 108.4, 63.6, 28.2, 26.0, 18.4, 11.7, —5.3.

MS (EI) m/z = 289 (M+).

77

Synthesis of 1-phenyl-3-methyl-tetrahydropyridazine(17)

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.139 g, 0.37 mmol) in toluene (1.8 mL), phenylhydrazine (717 11L, 7.30 mmol), and 5-
chloropent-l-yne (775 uL, 7.30 mmol). The tube was sealed and removed from the dry

box for heating at 80 °C for 24 h. The reaction was then allowed to cool to room

temperature, diluted with dichloromethane (20 mL), and saturated NaHCO3 solution was

added. The organic layer was separated. The aqueous layer was extracted with

dichloromethane (3 X 15 mL). The combined organics were washed with water, and the

final combined organics were dried over MgSO4, filtered, and dried in vacuo. This

yielded a dark brown oil, which was subjected to column chromatography on silica gel

using 4:1 petroleum ether:ether as eluent. The product45 was isolated in 32% yield
(0.400 g, 2.30 mmol) as yellow oil, which turned to red on standing. 1H NMR (499.7
MHz, CDCl3): 7.29 (t, 2 H, JHH = 4.1 Hz, 8.7 Hz, o-Ph), 7.22 (d, 2 H, JHH= 7.8 Hz, m-
Ph), 6.87 (t, 1 H, JHH = 7.4 Hz, p-Ph), 3.51 (t, 2 H, JHH = 6.1 Hz, NCHQ), 2.21 (t, 3 H,
JHH = 6.1 Hz, C(=N)CH2), 2.08 (m, 2 H, (=N)CH2CH2), 2.02 (s, 3 H, CH3). l3C{'H}
NMR (125.7 MHz, CDCI3): 148.3, 143.6, 128.8, 119.1, 113.5, 42.2, 25.6, 24.3, 19.0. MS
+
(EI) m/z = 174 (M ).

78

Synthesis of 2-methyltryptamine (20)

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.185 g, 0.49 mmol) in toluene (2.4 mL), phenylhydrazine (964 11L, 9.80 mmol), and 5-
chloropent-l-yne (1034 11L, 9.80 mmol). The tube was sealed and removed from the dry
box for heating at 80 °C for 24 h. The reaction then was allowed to cool to room
temperature. The hydrochloride salt (18) of the product precipitated during reaction. The
precipitate was washed with ethylacetate (50 mL), which contained crude 17 . To the

crude 18 was added NaOH (20%, 25 mL), and the product was extracted with
ethylacetate (3 X 20 mL). The combined organic layers were dried over Na2804, filtered,
and volatiles were removed under vacuum. To the resulting brown oil was added hexanes

(20 mL), and then HCI in ether until it reached pH ~ 2. A brown solid precipitated from

the solution. The solid was filtered and volatiles were again removed under vacuum.
Next, the solids were dissolved in dichloromethane (20 mL), and saturated NaHCO3
solution was added to the solution (pH ~ 7). The mixture was shaken, and the organic

layer was separated. The aqueous layer was extracted with dichloromethane (3 X 15 mL).

The combined organic layers were washed with water. The final organic layer was dried

over MgSO4, filtered, and volatiles removed in vacuo. This yielded 20 as a brown oil63

in 32% yield (0.400 g, 2.30 mmol). 'H NMR (499.7 MHz, 00013): 7.76 (br s, 1 H, NH),

79

7.85 (d, 1 H, JHH = 8.1 Hz, 7H-indole), 7.26 (d, 1 H, JHH = 5.6 Hz, 4H—indole), 7.18-
7.04 (m, 2 H, k, 5H-indole), 2.96 (t, 2 H, JHH = 6.6 Hz, 3-CH2), 2.84 (t, 2 H, JHH = 6.6
Hz, NHQCHQ), 2.38 (s, 3 H, 2-CH3), 1.74 (br s, 2 H, NHZ). 13C{]H} NMR (125.7 MHz,
CDC13): 135.3, 131.8, 128.8, 121.0, 119.2, 118.0, 110.2, 109.0, 42.5, 28.0, 11.8. MS (EI)

m/z = 174 (M+).

80

Synthesis of 2,5-dimethyl-3-propyl-NH-indole (21)

H
N
Me n

Pr
Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.029 g, 0.08 mmol) in toluene (375 uL), p-methylphenylhydrazine (0.183 g, 1.50
mmol), and l-hexyne (175 11L, 1.50 mmol). The tube was sealed and removed from the

dry box for heating at 80 °C for 16 h. The solution was then allowed to cool to room

temperature, taken inside the box, and excess ZnClz (0.602 g, 4.50 mmol) was added.

The reaction was heated at 100 °C for 16 h. After that, the solution was allowed to cool to
room temperature, diluted with ether, and passed through a pad of silica in a fritted
funnel. Volatiles were removed from the filtrate in vacuo. The resulting dark red oil was

subjected to column chromatography on silica gel with 1:1 hexaneszethylacetate as

eluent. The product was isolated as a red oil in 64% yield (0.180 g, 0.90 mmol). 1H NMR
(299.8 MHz, CDCl3): 7.61 (br s, 1 H, NH), 7.26 (s, 1 H, 4H-indole), 7.13 (d, l H, JHH=
8.1 Hz, 6H—indole), 6.91 (dd, 1 H, JHH = 1.4, 8.1 Hz, 7H-indole), 2.61 (t, 2 H, JHH = 7.3
Hz, 3-CH2), 2.43 (s, 3 H, 5-CH3), 2.33 (s, 3 H, 2-CH3), 1.63 (m, 2 H, CH3CH2), 0.94 (t,
3 H, JHH = 7.4 Hz, CHZCH3). l3C{]H} NMR (75.4 MHz, CDC13): 133.5, 130.9, 129.1,

128.0, 122.2, 118.0, 111.9, 109.7, 26.2, 23.8, 21.5, 14.1, 11.7. MS (EI) m/z = 187 (M+).

81

Synthesis of 2-methyl-5-fluoro—3-propyI-NH-indole (22)

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.029 g, 0.08 mmol) in toluene (375 11L), p-fluorophenylhydrazine (0.192 g, 1.50
mmol), and l-hexyne (175 11L, 1.50 mmol). The tube was sealed and removed from the

dry box for heating at 80 °C for 16 h. The reaction then was allowed to cool to room

temperature, taken inside the box, and excess ZnC12 (0.602 g, 4.50 mmol) was added.

The mixture was heated at 100 0C for 16 h. After that, the reaction was allowed to cool to
the room temperature, diluted with ether, and passed through a pad of silica in a fritted
funnel. Volatiles were removed from the filtrate in vacuo. The resulting dark red oil was

subjected to column chromatography on silica gel with 2:1 etherzpentane as eluent. The

product was isolated as a red oil in 70% yield (0.200 g, 1.05 mmol). 1H NMR (499.7
MHz, CDCl3): 7.61 (br s, 1 H, NH), 7.17-7.15 (dd, 1 H, JHH = 2.5, 9.9 Hz, 4H-indole),
7.14—7.11 (dd, 1 H, JHH = 4.4, 8.6 Hz, 7H-indole), 6.87 — 6.83 (dt, 1 H, JHH = 2.5, 9.0
Hz, 6H—indole), 2.63 (t, 2 11,ng = 7.7 Hz, 3-CH2), 2.35 (s, 3 H, 2-CH3), 1.63 (m, 2 H,
CH3CH2), 0.95 (t, 3 H, JHH = 6.5 Hz, CHZCH3). I3C{1H} NMR (125.7 MHz, CDCI3):
158.6, 156.7, 132.9, 129.3 (d, JCF = 9.7 Hz), 112.5 (d, JCF = 4.5 Hz), 110.5 (d, JCF= 9.7

Hz), 108.7 (d, JCF = 26.2 Hz), 103.3, (d, JCF = 23.6 Hz), 26.1, 23.7, 14.0, 11.7.

82

Elemental Analysis; Experimental (Calc.), C: 75.04 (75.36). H: 7.65 (7.38). N: 7.18

(7.32). MS (EI) m/z = 191 (M+).

83

Synthesis of 2-methyl-5-methoxy-3-propyl-NH-indole (23)

H
N
@1211:
MeO n

Pr
Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.057 g, 0.15 mmol) in toluene (750 uL), p-methoxyphenylhydrazine (0.421 g, 3.0
mmol), and l-hexyne (350 uL, 3.0 mmol). The tube was sealed and removed from the

dry box for heating at 80 °C for 16 h. The reaction then was allowed to cool to room

temperature, taken inside the box, and excess ZnC12 (0.602 g, 9.00 mmol) was added.

The mixture was heated at 100 °C for 16 h. After that, the reaction was allowed to cool to
the room temperature, diluted with ether, and passed through a pad of silica in a fritted
funnel. Volatiles were removed from the filtrate in vacuo. The resulting dark brown-red

oil was subjected to column chromatography on silica gel with 1:1 hexaneszethylacetate

as eluent. The product was isolated as red oil in 76% yield (0.460 g, 2.30 mmol). 1H
NMR (499.7 MHz, CDC13): 7.58 (br s, 1 H, NH), 7.25 (d, 1 H, JHH = 8.8 Hz, 7H-indole),
6.94 (d, 1 H, JHH = 2.5 Hz, 4H—indole), 6.76-6.72 (dd, 1 H, JHH = 2.5, 8.5 Hz, 6H-
indole), 3.85 (s, 3H, OCH3), 2.62 (t, 2 H.111“ = 7.4 Hz, 3-CH2), 2.32 (s, 3 H, 2-CH3),
1.68-1.59 (m, 2 H, CH3CH2), 0.96 (t, 3 H, JHH = 7.4 Hz, CHZCH3). 13C{]H} NMR

(125.7 MHz, CDC13): 153.7, 131.8, 130.4, 129.3, 112.1, 110.6, 110.2, 100.9, 56.0, 26.2,

23.7, 14.1, 11.8. Elemental Analysis; Experimental (Calc.), C: 76.62 (76.81). H: 8.85

(8.43). N: 6.34 (6.89). MS (EI) m/z = 203 (M+).

84

Reaction of 1,4-nonadiyne with phenylhydrazine to synthesize 24 and 25

Q. Q.

Bu

Nl’ M
/
Me /

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with 5
(0.040 g, 0.11 mmol) in toluene (525 uL), phenylhydrazine (204 1.1L, 2.10 mmol), and
nona-1,4-diyne (0.250 g, 2.10 mmol). The tube was sealed and removed from the dry box
for heating at 80 °C for 16 h. The reaction was then allowed to cool to room temperature,
diluted with ether, and passed through a pad of alumina in a fritted funnel. Volatiles were
removed from the filtrate in vacuo. The resulting dark red oil was subjected to column
chromatography on alumina. Isomer 24 eluted with 5:1 hexanes:ether as the first fraction.
After removing volatiles in vacuo, 24 was isolated in 17% yield (0.080 g, 0.35 mmol).

Isomer 25 eluted using 1 :1 hexanes:ether in the second fraction. After removing volatiles

in vacuo, 25 was isolated in 42% yield (0.203 g, 0.89 mmol). Isomer 24: 1H NMR (499.7
MHz, CDC13): 7.26-7.19 (m, 4 H, o,m-Ph), 6.83 (t, 1 H, JHH = 7.0 Hz, p-Ph), 6.04 (dd, 1
H, JHH = 6.6, 9.3 Hz, SH-pyridazine), 5.87 (d, 1 H, JHH = 9.9 Hz, 3H—pyridazine), 4.62
(m, 1 H, 6H—pyridazine), 2.06 (s, 3 H, 3-CH3), 1.61-1.47 (m, 2 H, 6-CH2), 1.28 (m, 4 H,
CH3CH2 and CH3CH2CH2), 0.84 (t, JHH = 6.9 Hz, 3H, CH3CH2). l3C{'H} NMR
(125.7 MHz, CDC13): 146.0, 142.8, 129.0, 127.4, 120.0, 119.6, 113.7, 51.0, 30.6, 26.2,
22.7, 21.2, 14.0. MS (131) m/z = 228 (M+). Isomer 25: 1H NMR (499.7 MHz, CDC13):
7.46-7.32 (m, 5 H, Ph), 6.00 (s, 1 H, 4H—pyrazole), 2.58 (t, 2 H, JHH = 8.0 Hz, 5-CH2),

85

2.29 (s, 3 H, 3-CH3), 1.55 (m, 2 H, CHZCHz), 1.25 (m, 4 H, CH3CH2CH2 and
CH3CH2CH2), 0.84 (t, 3 H, JHH = 7.1 Hz, CHZCH3). l3C(1H} NMR (125.7 MHz,
CDCl3): 148.9, 144.6, 140.0, 129.0, 127.4. 125.3, 105.2, 31.4, 28.5, 26.2, 22.3, 13.9,

13.6. MS (El) m/z = 228 (M+).

X-ray Crystallography

Crystals grown from concentrated solutions at room temperature were moved quickly
from a scintillation vial to a microscope slide containing Paratone N. Samples were
selected and mounted on a glass fiber in wax and Paratone. Data were collected using a
Bruker CCD diffractometer equipped with an Oxford Cryostrearn low-temperature
apparatus operating at 173 K. The data were processed and reduced utilizing the program
SAINTPLUS supplied by Bruker AXS. Data reduction was performed using the SAINT
sofiware. Scaling and absorption corrections were applied using SADABS multi-scan

technique supplied by George Sheldrick. The structure was solved by the direct method

using the SHELXS-97 program and refined by the least squares method on F2, SHELXL-

97, incorporated in SHELXTL-PC V 6.10.

86

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Alex, K.; Tillack, A.; Schwarz, N.; Beller, M. Tet. Lett. 2008, 49, 4607.
Robinson, B. The Fischer Indole Synthesis, Wiley & Sons: Chichester, UK, 1982.
Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875.
Hulcoop, D. G.; Lautens, M. Org. Lett. 2007, 9, 1761.

Barluenga, J .; Jimenez-Aquino, A.; Valdes, C.; Aznar, F. Angew. Chem. Int. Ed.
2007, 46, 1529.

Patil, S.; Buolamwini, l. K. Curr. Org. Synth. 2006, 3, 477.

Lu, B. Z.; Zhao, W. Y.; Wei, H. X.; Dufour, M.; Farina, V.; Senanayake, C. H.
Org. Lett. 2006, 8, 3271.

Hostyn, S.; Maes, B. U. W.; Van Baelen, G.; Gulevskaya, A.; Meyers, C.; Smits,
K. Tetrahedron 2006, 62, 4676.

Fayol, A.; Fang, Y. Q.; Lautens, M. Org. Lett. 2006, 8, 4203.
Djakovitch, L.; Dufaud, V.; Zaidi, R. Adv. Synth. Catal. 2006, 348, 715.
Ambrogio, 1.; Cacchi, S.; Fabrizi, G. Org. Lett. 2006, 8, 2083.

Abbiati, G.; Arcadi, A.; Beccalli, E.; Bianchi, G.; Marinelli, F.; Rossi, E.
Tetrahedron 2006, 62, 3033.

Cacchi, S.; Fabrizi, G. Chem. Rev. 2005, 105, 2873.

Ackermann, L.; Kaspar, L. T.; Gschrei, C. J. Chem. Commun. 2004, 2824.
Lipinska, T. M. Tetrahedron 2006, 62, 5736.

Garg, N. K.; Stoltz, B. M. Chem. Commun. 2006, 3769.

Schmidt, A. M.; Eilbracht, P. J. Org. Chem. 2005, 70, 5528.

Tietze, L. F.; Modi, A. Med. Res. Rev. 2000, 20, 304.

Banerjee, S.; Barnea, E.; Odom, A. L. Organometallics 2008, 27, 1005.

88

41.

42.

43.

44.

45.

46.

47.

48.

49.

50.

51.

52.

53.

54.

55.

56.

57.

58.

Kim, I. T.; Elsenbaumer, R. L. Tetrahedron Lett. 1998, 39, 1087.

Raines, S.; Kovacs, C. A. J. Heterocycl. Chem. 1970, 7, 223.

Herz, W.; Dittmer, K. J. Am. Chem. Soc. 1947, 69, 1698.

The zirconium derivative has the geometry described in a structure determined by
X-ray diffi'action and is spectroscopically similar. Barnea, E.; Odom, A. L. Dalton.
Trans. 2008 4050.

Benincori, T.; Brenna, E.; Sannicolo, F. J. Chem. Soc. Perkin Trans. 1. 1991, 2139.
Grandberg, I. 1.; Kost, A. N.; Terentev, A. P. Russ. J. Gen. Chem. 1957, 27, 3378.

Similar dihydropyridazine compounds are known. For references see: Kaneko, C.;
Tsuchiya, T.; Igeta, H. Chem. Pharm. Bull. 1974, 22, 2894.

Crosslanl; Kelstrup, E. Acta. Chem. Scand. 1968, 22, 1669.

For some examples of similar insertion of alkynes into transition metal-nitrogen
bonds see: Katayev, E.; Li, Y. H.; Odom, A. L. Chem. Commun. 2002, 838.

Boncella, J. M.; Eve, T. M.; Rickman, B.; Abboud, K. A. Polyhedron 1998, 17,
725.

Vanderlende, D. D.; Abboud, K. A.; Boncella, J. M. Inorg. Chem. 1995, 34, 5319.
Villanueva, L. A.; Abboud, K. A.; Boncella, J. M. Organometallics 1992, 1 I, 2963.

Kemmitt, R. D. W.; Mason, S.; Moore, M. R.; Fawcett, J .; Russell, D. R. J. Chem.
Soc. Chem. Commun. 1990, 1535.

Hydroamination of alkynes using lanthanides also involved similar insertion. For a
review see: Hong, S.; Marks, T. J. Acc. Chem. Res. 2004, 37, 673.

Bergman, J .; Carlsson, R. J. Heterocyclic Chem. 1972, 9, 833.

Similar Michael type reaction is known with acetic acid. For references see: Ferres,
H.; Harndam, M. S.; Jackson, W. R. J. Chem. Soc, Perkin Trans. 1973, 936.

Alexande.Cw; Jackson, W. R.; Hamdam, M. S. J. Chem. Soc., Chem. Commun.
1972, 94.

Verkruijsse, H. D.; Hasselaar, M. Synthesis 1979, 292.

89

59.

60.

61.

62.

63.

Brandsma, L. Preparative Acetylenic Chemistry, Elseim Publishers: Amsterdam-
London-New York, 1971, 137.

Bradley, D. C.; Thomas, I. M. J. Chem. Soc. 1960, 3859.
Jackson, A. H.; Smith, A. E. Tetrahedron 1965, 21, 989.

Minakata, S.; Kasano, Y.; Ota, H.; Oderaotoshi, Y.; Komatsu, M. Org. Lett. 2006,
8, 3693.

Jackson, A. H.; Smith, A. E. J. Chem. Soc. 1964, 5510.

90

CHAPTER 3

Iminohydrazination of alkynes:
scope, mechanistic investigation, and applications
towards pyrazole synthesis

3.1 Introduction

Iminohydrazination is the conversion of an alkyne to an (LB-unsaturated B-
aminohydrazone, making both C~C and C—N bonds in a single step. This is a new
multicomponent reaction (MCR) between an alkyne, 1,1-disubstituted hydrazine, and

isonitrile in the presence of a catalyst.

Multicomponent reactions are valuable tools for the preparation of complex
structures from simple starting materials. Multicomponent reactions are well suited for
the rapid and highly atom-economical assembly of large compound libraries. As a

consequence, the application of MCR to the drug discovery process has drawn

. . . . . 1,2
con51derable attention in recent years. A few of the earlier examples are Mannich,

Strecker,3-6 Hantzsch,7 and Biginelli8 reactions. In 1959, Ugi and co-workers reported

the one-pot condensation of a carbonyl (aldehyde or ketone), amine, carboxylic acid, and

isonitrile (Scheme 3.1). This reaction, now referred to as the Ugi 4-comp0nent reaction

91

 

 

(Ugi-4CR), provides an efficient method to construct functionalized

acylamidoacetamides. Later, this protocol was adopted by Guanti et al. for the synthesis

. . . . . . 10
0f a-amino acrd derivatives in a very stereoselective manner.

Scheme 3.1 Ugi 4-component reaction

 

0 o
0 NR1 34k 3»”\ ,R1
2JL H NR1 2k R OH R N 4
+ 2 —-——> ¢
R H R H R4NC F,2J\WNHR

0

Further development in this area involves transition metal catalyzed MCR. Transition

11,12 13 14 15 .16 .17-21 22 23
metals such as Pd, Cu, Ag, Zn, N1, T1, Zr, and Rh have been

effectively used for different multicomponent transformations. One example of Pd

catalyzed MCR is shown in Equation 3.1.

 

 

 

 

T T
1 R2 [R1
'1‘" 5°/ N
0
RZJ de )‘R5 5 ,R imine
+ O R\r.‘N 2
_ -2 /‘ .b—R
3 -— 4 : /‘\
R __ R . . R4 <31)
, 4 atm CO, EtNPr’2 aCId , 3
chlorlde ( R
O
R5 CI alkyne

In the previous chapters, we have shown that Group 4 metal complexes can be widely

used in catalytic transformations of organic molecules, e.g., hydroamination and

92

 

 

 

 

hydrohydrazination reactions. They can be used in MCR as we11.17-22 For example,

Odom and co-workers have explored the titanium-catalyzed 3-component coupling

reaction between alkyne, amine, and isonitrile to generate 01,13-unsaturated B-iminoamines

 

 

. 21
(Equation 3.2).
\ NMe2
01- 1.11
|_
Ph : Me / ”l/ | e2
100/0 / “"N
+ \
Me
PhNH2 =
toluene, 100 °C
+ l 72%
CN-Bu

But

I

HN

Ph—N\ />

Me Ph

(3.2)

As an extension of this work, a new multicomponent reaction has been carried out

between alkyne, 1,1-disubstituted hydrazine, and isonitrile to generate (1.13-unsaturated B-

. . . . 24 . . .
aminohydrazone in the presence of pyrrolyl-based titanium catalysts. This reaction 1S

formally the iminohydrazination of the alkyne. The results of this reaction, mechanistic

studies, and applications are discussed in detail in the following sections of this chapter.

93

3.2 Results and Discussion
3.2.] Iminohydrazination Results

Iminohydrazination is a modification of alkyne hydrohydrazination. In
hydrohydrazination reaction, an alkyne is allowed to react with a 1,1-disubstituted
hydrazine in the presence of a catalyst to generate a hydrazone. In iminohydrazination, an
alkyne is reacted with 1,1-disubstituted hydrazine and isonitrile in the presence of a

catalyst to generate 01,0-unsaturated B-aminohydrazones. For this reaction, three different

titanium-based catalysts were used: Ti(NMe2)2(dap)2 (1), where dap is 2-(N,N-
dimethylaminomethyl)pyrrolyl, Ti(NMe2)3(bap) (28), where bap is bis-2,5-(N,N-

dimethylaminomethyl)pyrrolyl, and Ti(NMez)2(SC6F5)20\lHMe2) (29). The Hdap ligand

was synthesized by the reaction of one equivalent each of pyrrole, formaldehyde, and

dimethylamine hydrochloride. The ligand was isolated in 77% yield (Equation 3.3).25
Catalyst 1 was then synthesized by adding two equivalents of Hdap to Ti(NMe2)4 and

isolated in 95% yield (Equation 3.4).26

94

H H
U + H H + Me2NH-HCI 77% [)4 (3.3)

Hdap

 

NMe2

H
N NMez Et20 €Nhl . l’ 1\NM82
Ti(NMe2)4 + 2 [Ly—J 95% M (3.4)
62
M:2N1l:)N;\>

 

The Hbap ligand was synthesized by adding two equivalents each of formaldehyde

and dimethylamine hydrochloride to one equivalent of pyrrole and isolated in 82% yield

(Equation 3.5).27

C)

H H
N /U\ RT, 12 11 MezN N

Hbap

 

Catalyst 28 was synthesized in 92% yield by adding one equivalent of Hbap to

Ti(NMe2)4 (Equation 3.6). The solution NMR spectrum reveals that the two arms of the
bap ligand are equivalent to each other. However, as shown in Figure 3.1, the solid state
structure shows that only one arm is coordinated. The uncoordinated amine nitrogen is

4.1 A away from titanium. This suggests that the equivalency of the two dimethylamine

donors in solution is likely due to fast exchange processes.

95

NMe
MeZN (Ti 2)3

/
MezN Et20 N \NMeZ

Ti(NMe2)4 * \DJNMez 920/ T M (36)
I o
28

 

\ZI

Catalyst 29 was synthesized by adding two equivalents of C6F5SH to Ti(NMe2)4 and

isolated in 65% yield (Equation 3.7).26

 

SH / F NM
\ 5 e
Ti NMe + "'Ti—NMe 3.7
( 2)4 \, 65% \ S/f 2 ( )
F5 | NHMe2
29

96

Figure 3.1 Solid-state structure of Ti(NMe2)3(bap) (28) from X-ray diffraction.

    

'1
mm ~§”4
«ES .
4% ,
‘ \ [Mk V all} {all}
it", ' 3 m3) Vii '1 W?‘
t 74, 70,“, M2, NM) ,
~ NM) _\\ '
v\‘ \‘
@b
1‘ .7 «a
‘§Illp‘ 33'

This new iminohydrazination reaction tolerates a wide range of substrates, including
terminal and internal alkynes with aliphatic and aromatic isonitriles (Table 3.1). In all
these reactions, 10 mol% catalysts 1 and 28 were used. The reactions are more facile with
terminal alkynes and alkyl isonitriles. Interestingly, if diphenylhydrazine is used, only a
small amount of the product and a significant amount of diphenylarnine are obtained.
Note that in the iminoamination reaction, which is a 3-component coupling of alkyne,

amine, and isonitrile, we did not observe the expected 3-component coupling product

. . . 21 . . . .
when cyclohexyllsomtrlle was used. Immoammation required a quaternary carbon

adjacent to the nitrogen atom in the isonitrile. However, in the present study of

97

iminohydrazination, the expected product is formed even with cyclohexylisonitrile. The
need for an isonitrile having a quaternary carbon adjacent to the nitrogen atom is
eliminated by using hydrazine as a substrate. Therefore, this process can be generalized
for a wide range of substrates. The product yields varied from 12—73%.

Table 3.1 Examples of alkyne iminohydrazination

 

 

 

 

 

 

 

 

 

 

 

3
1 2 R\ 5 10 mol% [Ti] R3\ R5HN
R : R + lN—NH2+ CN—R 4v ’N_N\ /
4
R ’—<
R R1 R2
[Ti] = Ti(dap)2(NMe2)2 (1) or Ti(NMez)3(bap) (28)
Yield
Entry R], R2 R3, R4 R5 Conditionsa Product (%)
ButHN
1 Bu",H Me, Me Bu’ A, 16h MeZNTN)\ /) 63
Bun 30
M MT TH‘Q fl CyHN m
Me N—N
2 Bu",H Me,Me Cyb A,16h 2 \ / 73
EU" 31
ArHN
. M N—N
3 Me, Ph Me, Me A,‘ B, 43h 92 \ / 15
Me Ph 32
ButHN
4 Bu”,H Ph, Me Bu’ A,16h WWW—NR /> 27
EU" 33
ButHN
t Me2N—N /
5 H, Ph Me, Me Bu C.16h 43
Ph
34

98

Table 3.1 (Cont’d.)

 

ArHN
MezN—N >
n Me, c \ /
6 Bu ,H Me Ar A,I6h B n 12
u
35

 

a
A = 10 mol% l in toluene at lOO °C, B = 10 mol% I in toluene at I30 °C, C = 10 mol% 28 in

b c
toluene at 100 °C. Cy = cyclohexyl. Ar = 2,6-dimethylphenyl

The catalytic activity of 29 in iminohydrazination reaction was also explored.
Unfortunately, 29 did not generate the desired 3-component coupling product except for
the substrates in Entry 5 of Table 3.1, where the quite reactive alkyne phenylacetylene
was used. The reaction with phenylecetylene produced a significant amount of
hydrohydrazinated product, making 29 less effective than 28. In this case, as shown in
Equation 3.8, the major product was dimethylhydrazone of phenyl acetaldehyde (anti-
Markovnikov product) and the minor product was dimethylhydrazone of acetophenone
(Markovnikov product). In addition, 29 also showed some activity for the substrates in
Entry I, but produced a 4-component coupling product that corresponds to the mass of

two isonitriles, one alkyne, and one hydrazine (Equation 3.9).

99

 

 

 

 

Ph : H
+ 10 mol% 29
Me2NNH2 ;
+ toluene, 100 °C
CN—But 16 h
Bun : H
+ 10 mol% 29
MezNNHZ ;
+ toluene, 100 °C
t 16 h
CN—Bu

t

Bu HN N,NMez
Me2N— N\ / A .
ph Me Markovnikov
Ph A A' product
+ t + (3.8)
Bu HN MezN.N
M€2N_N\ / anti-Markovnikov
H product
P“ 8 Ph 3'
3-component Hydrohydrazinated
coupling product product
3.321
[A] / [B] = 0.162 [A'1/[B'] = 0.333
4-component coupling product (3.9)

100

3.3 Mechanistic Investigation
3.3.1 Pathway via l,2-insertion

We proposed two possible mechanisms for iminohydrazination. The first one was a
l,2-insertion pathway. This involved l,2-insertion of an alkyne into a titanium

hydrazido(l—) intermediate, a pathway extensively studied by Marks and co-workers for

. 28 . . . . . . . . . .
amlde. If the isonitrile traps the resulting vmyl intermediate Vla 1,1-insertion, a 3-

component coupling product would result according to Scheme 3.2.

Scheme 3.2 Possible l,2-insertion pathway for the iminohydrazination reaction

3

 

R HN
M62N_N\ />
R1 R2 Ti(dap)2(NMez)2
M NNH
6% MezNNHz
[Tll—NH
n \ /
Bu MezN
H'T‘JXH “H : Bun
Me2N t
HN
/ Tl
\IJZN‘ ‘\ H N \NMez
rn] [Ti]: U4
Bu NC

For the above mechanism, the formation of a hydrazido(1—) intermediate is necessary.
If the alkyne inserts into this intermediate, then reactions with trimethylhydrazine should

generate an iminohydrazination product similar to Entry I in Table 3.1. To verify this

101

point, a 3-component coupling reaction with I-hexyne, N,N,N'-trimethylhydrazine, and
tert-butylisonitrile was attempted (Equation 3.10). However, no reaction was observed
when monitored by GC/FID. Therefore, it is unlikely that the iminohydrazination
reaction involves a 1,2-insertion pathway. Alternatively, the reaction may involve a
hydrazido(2—) intermediate and follow a mechanism similar to the zirconocene-based

hydroamination of alkynes established by Bergman which is discussed in the next

 

 

section.
Bun : H
.4.
Me\ /Me 10 mol% 1
/N-N\ > No reaction (310)
H Me 100 °C, 16 h
+
t
CN—Bu

3.3.2 [2 + 2]-cycloaddition mechanism

An alternative mechanistic pathway for the iminohydrazination reaction can be

.. . . 2930 .
ant1c1pated followmg the Bergman mechanism for znrconocene-catalyzed

hydroamination as shown in Scheme 3.3. Catalyst 1 forms a titanium hydrazido(2—)
intermediate, which undergoes [2 + 2]-cycloaddition with alkyne to form an
azatitanacyclobutene. This cycloaddition step is followed by 1,1-insertion of isonitrile

forming a new Ti—C bond. The five-membered metallacycle then rearranges to form an

isolable intermediate 36. Compound 36 finally undergoes intermolecular protonolysis

generating the 3-component coupling product.

Scheme 3.3 Possible mechanistic pathway of iminohydrazination by l for Entry 1 in

   
   

        
  

Table 3.]
R3H
e
2 2 R1 R2
TMez
\ N PM” 1 Ti(dap)2(NMe2)2
\ N\||_/N_-‘ 2 100°C NMe2
TI tonol sis '
/ \ J) R pro y N XNNH
1 n NMez N" ll. 92 2
R =Bu I 36 [T1]—NH
R = MezN
3_ t
R - Bu proton transfer
94% room temp [2 + 2]-cycloaddition |:z1—:—R2
/N\Me2 ”Meg room temp
HN\Uil’N R1HNMe2
RENM MezNNHZ
R2 “"""’2"'<[T\11’\Z’R
Hydrohydrazination
room temp
1,1-insertion MeZNN
2
R3Nc RJJK/R
[Ti] 2 Ti(dap)

In an attempt to isolate an intermediate, a reaction was carried out involving 1 with 1

equivalent each of l-hexyne, 1,1-dimethylhydrazine, and tert-butylisonitrile. The reaction

was very facile and generated Ti(NNMe2)(dap)[N(But)CHCHC(Bun)N(NMe2)-k2N]

l03

(36), at room temperature (Equation 3.11). The compound was isolated in 94% yield with

respect to limiting hydrazine.

 

 

NMez
Bun : H NMeZB uI’i
Ti(dap)2(NMe2)2+ H2N+NMe2 mluene =QZ>ITI1N<NjBU (3.11)
1 + 1 113“ 11. .
CN-Bu ° 2368

The structure of 36 was solved by X-ray diffraction and is shown in Figure 3.2. It has

many features in common with another structurally characterized titanium

dimethylhydrazido(2—) complex, Ti(NNMe2)(bpy)(dpma), where dpma is N,N-

di(pyrrolyl-a-methyl)-N-methylamine.3I Both have approximately linear terminal

hydrazido(2—) Ti—N—N angles, which measured I69.6(2)° in 36.

lO4

Figure 3.2 Structure of hydrazido(2—) complex 36 from X-ray diffraction. Selected bond
distances (A) and angles (°): Ti—N(2), 1.709(3); Ti—N(3), 2.077(2); Ti—N(4), 2.055(3);
Ti—N(1), 2.119(3); Ti—N(11), 2.323(3); N(2)—N(21), 1.403(4); N(3)—N(31), 1.457(3); Ti—
N(2)—N(21), 169.6(2).

AK

. /

I/
\
E.

l'

-
_

 

The Ti=N(hydrazido) bond distance in 36 is 1.709(3) A and is in the usual range for a

titanium-nitrogen double to triple bond. The hydrazido(2—) N—N distance of 1.402(4) A is

slightly shorter than an N—N single bond, which is 1.451 i 0.005 A in hydrazine.32 The

shortening of the hydrazido(2—) N—N distance is perhaps due to contribution from the
isodiazene resonance form (Figure 3.3). While the hydrazido(2—) form is favored for the
electropositive titanium center, which is very reducing as titanium(Il), for more weakly
E-donating metal centers the isodiazene form strongly prevails. The isodiazene

resonance form is known to be favored in many other compounds. For example, in an

105

isodiazene iron porphyrin complex, the N—N bond distance is 1.232(5) A,” indicating a

bond order of ~2.0 (discussed in more details in Section 4.2, Chapter 4).34

Figure 3.3 Possible resonance forms of 36. (For simplicity, the other ligands are not

shown).
Me\ [Me Me\(3,Me
1" (9H
11 .___. i‘
Ti4+ 112+
hydrazido(2—) isodiazene

Most often, N is planar in hydrazido(2—) complexes and only a few examples with
pyramidalized nitrogens have been structurally characterized.35 The angles around N13 in
36 sum up to 335.5(3)°, only slightly higher than that expected for an sp3 hybridized
nitrogen in NR3 compound (328.0°). Therefore, the dimethylhydrazido(2—) complex of
titanium (36) has a pyramidalized NB’ consistent with the preferred hydrazido(2—)

. . . 36 3
resonance form in these early metal derlvatives.

The overall geometry of the five-coordinate complex, 36, is intermediate between a
square pyramidal and a trigonal bipyramidal, the former is slightly more favored. The

complex 36 has a continuous symmetry parameter value of r = 0.36, where T = 0

. . . . . 38,39
represents a square pyramid and I = 1 represents a trigonal bipyramid. The nacnac

ligandzo’40 of 36, although quite unsymmetrically substituted, is symmetrically bound to

106

titanium, where the Ti—N(NMe2) and Ti—N(But) distances are 2.080(3) and 2.055(3) A,

respectively. The other C—C and ON distances within the 6-membered ring are also

consistent with a highly delocalized system.

Examination of the 1H NMR spectrum of this hydrazido(2—) complex reveals a slight

broadening of the methyl groups associated with the multiple bonded ligand due to

relatively slow exchange. The barrier associated with the exchange of the two methyl

—1 . .
groups has been measured as 12 kcal mol usmg variable temperature NMR

spectroscopy. Apparently, the barrier is associated with steric interactions between the
hydrazido(2—) methyl groups and groups on the nacnac ligand, an observation also

supported by the corresponding Density Functional Theory (DFT) calculations.

Attempts to increase the yield of 36 by adding more than one equivalent (two

equivalents) of MezNNHz to 1 yielded a new dinuclear compound Ti2(dap)3(p2:[]l,l]2-

NNMe2)(u1:[]l-NHNM62) (37), which has two bridging hydrazido(2—) ligands and one

dap protolytically replaced with a hydrazido(l—) ligand (Equation 3.12). The compound
has been isolated in 61% yield as yellow crystals from a 1:1 solution of dichloromethane
and pentane. From the structure of the isolated dinuclear compound, it is obvious that at
least one of the clap ligands is cleaved during the reaction (Figure 3.4). Hence one dap is

protolytically labile in the presence of 1,1-dimethylhydrazine.

107

Mez

 

/
_ toluene /N\\‘, 3 12
TI(dap)2(NMe2)2 + 2 MezNNHz +7 (dap)2Ti\N/TI(NHNMe2)(dap) ( - )
RT 12 h
’ \
61% N
37 M62

Figure 3.4 ORTEP representation of Ti2(dap)3(u2:nl,nz-NNMe2)2(u1:nl-NHNMez)
(37) at 50% probability level.

AN

N

J"
i

 

108

3.3.3 Kinetic studies

To further elucidate the role of 36 in the iminohydrazination reaction, the rate of the

catalysis with 36 was studied and compared to the rate observed with 1. The reactions

were monitored using 1H NMR setting the probe temperature at 100 °C for 10 h. The

overall yield of the reaction varied from 55—100% depending on the type of the reactions
studied (Table 3.2). The progress of the reaction was monitored vs time with respect to an
internal standard. The percent yield of the product is plotted vs time, and the data are fit

to a first order equation using the scientific graphing program OriginPro 7.5. The

equation used for the plots was Y, = inf + (Y0 — Yinf) x exp (—k0bst) where Yinf =
product yield at time infinity, Y0 = product yield at initialization, and kobs = the rate

. . . . 4l
constant, I = time in minute, and Y, = amount of the product formed at time t. The rates

are based on the average of four kinetic runs, and the error is calculated to the 99%

confidence limit. The results of the kinetic experiments are shown in Table 3.2.

The rate of the reaction was studied using 10 mol% of Ti(dap)2(NMe2)2 (1), as shown
in Case A in Table 3.2. A graph of percent yield versus time (min) has been plotted, and a

representative plot is shown in Figure 3.5. The kobs value was found to be (1.07 i 0.42) x

10—4 s_l. The remaining plots are shown in Appendix B (Figures Bl.l to Bl.3). It is

noteworthy that the yield of the reaction was only 55—60%. The relatively low yield for

this reaction is due to the formation of the titanium dinuclear complex 37, which is not

109

kinetically competent (vide infra). The in situ generation of this complex deactivates the

precatalyst 1, which may be the reason for the low product formation.

Figure 3.5 Representative plot for the catalysis with Ti(dap)2(NMe2)2 (1).

  
 
  

 

 

 

 

 

 

60 -
Exp 930
10% Ti(dap)2(NMe2)2
50 -
Data: Data1_B
Model: myeqn1
40 - Weighting:
2 y No weighting
it; ChiAZIDoF = 0.78358
go 30 _ R02 = 0.99404
yO 13.4 $0
. ; yinf 57.32759 10.24095
. -1
20 _ /l' k 0.00705 mIn 10.00013
/_ k 1.18E—4 s'
I
10 l v I T | ' l f l ‘ I ' I
0 100 200 300 400 500 600

time (min)

The intermediacy of the titanium hydrazido(2—) complex 36 in the catalytic cycle was
probed by studying the reaction as shown in Case B in Table 3.2. A graph of percent

yield versus time (minute) is shown in Figure 3.6. The individual plots for the other

reactions are given in Figures 32.] to 82.3. The kobs value for 36 was determined to be

110

(0.98 i 0.11) x 10_4 s—l. The rate constants for catalysis involving 36 are similar to those

of 1 within the error range. This suggests that 36 is an intermediate of the reaction. Based
on all these observations, we propose that the mechanistic pathway for

iminohydrazination reaction involves the following steps prior to the formation of 36: i)
formation of [ll-hydrazido(2—) intermediate, ii) [2 + 2]-cycloaddition of alkyne, iii) 1,1-

insertion of isonitrile and proton transfer to generate 36. Compound 36 was generated at
room temperature, and it contains one molecule of the product as a ligand. The required
temperature for the iminohydrazination reactions was 100 °C. This suggests that all the
steps prior to the formation of 36 are fast, and the protonolysis step to liberate the final

product is the slowest step in the formation of the iminohydrazination product.

11]

Figure 3.6 Representative plot for the catalysis with 36.

  
  

 

 

 

 

 

 

 

80 4
Exp 927
1 10% Ti(hydrazido)
70%
60 J Data: Data1_B
Model: myeqn1
E Weighting:
f; 50 - y No weighting
o\ Chi"2/DoF = 0.13034
R"2 = 0.99916
40 yO 3.11207 i0.68269
7 yinf 76.97504 10.26882
J
r k 0.00591 min‘1 10.0001
30 ‘ k 0.9954 s."1
fir I ' T 1 I ' I 1 I
0 100 200 300 400 500
time (min)

To further verify this mechanism, the reaction of 36 with 10 equivalents of 1,1-

di rT‘lethylhydrazine was studied kinetically (Case C, Table 3.2). A graph of percent yield

VerSUS time (min) is shown in Figure 3.7. The value of kobs was found to be (1.11 i 0.30)

>< —4

1 O s_l. This suggests that the protonolysis step is the rate determining for the

Fe - . . . . .
ac tlon. Once again, the plots for the other reactions are in the appendix (Figures 831 to

133-3).

112

Figure 3.7 Representative plot for the reaction of 36 with 1,1-dimethylhydrazine.

% yield

 

 

 

 

 

100 _ Exp 951 ’
Ti(hydrazido) + 10 MeZNNHZ /’
Jr"
90 -1 .1 ,l'
2"]
80 — I Data: Data1_B
’ Model: myeqn1
7O - /. Weighting:
/' y No weighting
,' Chi"2/DoF = 0.29418
60 ‘ 1" R"2 = 0.99914
," yO 3584991046327
_ F yinf 1190315911 .59389
50 ,
,1" k 000651000025 min'1
40 ‘ ' k 1.08E-4 s‘1
l l l l T l l
0 50 100 150 200 250
time (min)

113

 

Table 3.2 Rate Constants and conditions for kinetic experiments

 

 

 

 

 

 

 

 

 

 

H : Bu"
4.
Me\ 10 mol% Ti(dap)2(NMe2)2 (1) ButHN
Case A N-NH2 ; Me2N—N /
“he 100 °C, Toluene-d8, 10 h \
+ Bu"
1‘ 30
CN-Bu
H : Bu"
4.
Me. 10 mol% 36 Bu’HN
Case B N—NH2 = MezN—N /
“he 100 °C, Toluene-d8, 10 h \
+ Bun
t 30
CN-Bu
t
36 100 °C, Toluene-d8, 10 h BU HN
Case C + 7‘ MezN—N >
Me\ \ /
10 equiv. N-NH2 n
the B“ 30
H : Bun
+ 10 mol% 36 t
Me\ 10 mol% Hdap Bu HN
Case D N—NH2 #1 MezN—N /
Me 100 °C, Toluene-de, 10 h \
+ Bun
t 30
CN-Bu '
concentration (M)
Reaction [figs --1
Catalyst Hdap MezNNHz (X 10 s )
Case A 0.06 —— 0.6 1.07 i 0.42
Case B 0.06 — 0.6 0.98 1 0.1 1
Case C 0.06 — 0.6 1.11 1 0.30
Case D 0.06 0.06 0.6 1.19 i- 0.23

 

ll4

The precatalyst 1 contains two dap ligands. Interestingly, in the intermediate 36, only
one dap ligand is present. This suggests that one dap is lost prior to the formation of 36
and was present in the reaction medium. Hence we investigated the effect of excess Hdap

on the rate of the catalysis. Kinetic reactions were carried out as shown in Case D, Table

3.2. The plots are shown in Figure 3.8 and Figures 34.1 to 84.3. The value of kobs was

found to be (1.19 1 0.23) x 1041 s". This is similar to the kobs value of Case A in Table

3.2 within error, where the catalysis involves precatalyst 1. This indicates that there is

essentially no effect of additional Hdap ligand on the reaction rate.

Figure 3.8 Representative plot for the catalysis with 10 mol% of 36 and Hdap.

  
  

 

 
 

 

 

 

 

90-
Exp 994
10% Ti(hydrazido) + 10% Hdap
80-
-i
70-
Data: Data1_B
Model: myeqn1
1: 60- Weighting:
E y u‘ y No weighting
\Z‘ ." Chm/06F = 0.09293
° 50‘ I: R"2 = 0.99949
g yO 28722311019496
40 ,i' yinf 82735391009034
, f k 0007161000005 min'1
30- I k 1.19E-4 s'1

 

T f‘r V

. . fi .
300 400 500 600
time (min)

f I ' I
0 1 00 200

”5

The intermediacy of dinuclear compound 37 in the catalytic cycle was also

investigated. The reactions were carried out in a similar way to Case A, Table 3.2.

However, compound 37 yielded only 22% of the desired product, and the kobs value for

this reaction was 4.8 x 10"6 s“1 (Figure 85.1). This shows that compound 37 is not

kinetically competent to be involved in catalysis involving 1. Instead, 37 is perhaps a

mode of catalyst deactivation.

The dependence of the reaction rate on catalyst concentration was also studied. The

reactions were carried out using the conditions in Table 3.3. The progress of the reactions

was plotted vs time, and the resulting kobs values are shown in Table 3.3 (Figures B6.l,

B62, B63). Next, the individual kobs values were plotted vs catalyst concentration (M).
A straight line is obtained with R2 = 0.999 (Figure 3.9), suggesting a first order

dependence of kobs on catalyst concentration.

116

Table 3.3 Observed rate constant vs catalyst concentration

 

 

 

 

H : Bun
+ t
- Bu HN
Me\ x mol% Ti(da (NMe (1)
N—NHZ p)2 22 > MezN—N\ /
Me 100 °C, Toluene-d3, 10 h >-—’
+ Bun
CN-But 3°
0 —4 -1
Entry X mol/o Catalyst conc. (M) kobs (x 10 s )
1 15 0.09 1.79
2 10 0.06 1.19
3 5 0.03 0.61
4 2.5 0.015 0.34

 

Figure 3.9 Dependence of kobs on catalyst concentration

 

 

 

 

 

2.0
y = 19.37x + 0.037
2
1-6' R =0.999
i“
W 1.2 ~
'1’
O
S
g 0.8 .
O
-k
0.4 .
0.0 . . . .
0 0.02 0.04 0.06 0.08

Concentration (M)

”7

3.3.4 Overall mechanism for Iminohydrazination reaction

For iminohydrazination, the proposed catalytic cycle begins with the generation of a
titanium hydrazido(2—) complex, followed by [2 + 2]-cycloaddition to generate an
azametallacyclobutene intermediate, which after protonolysis yields the
hydrohydrazination product (Scheme 3.3). Isonitrile insertion forms a 5-membered
metallacycle, which, following a proton rearrangement, yields the isolable titanium

hydrazido(2—) complex 36. Compound 36 undergoes protonolysis at 100 °C with

MezNNHz to yield the product regenerating the active species.

3.3.5 Experimental observations on regioselectivities

The multicomponent reaction between phenylacetylene, 1,1 -dimethylhydrazine, and
tert—butylisonitrile generated both hydrohydrazination and iminohydrazination products.
Moreover, the products were obtained as mixture of regioisomers. The ratios of the
isomers were obtained from the GC/FID of the crude reaction mixture (Table 3.4). In all
these reactions, the anti-Markovnikov product was the major product with the phenyl
group in the 2-position of the 1,3-hydrazonylimine (same as Entry 5, Table 3.1). The
reaction was repeated six times using 1 as catalyst. The ratio of iminohydrazination
products was found to be 0.453 t 0.117 (99% confidence level, 0:5), with the range from
0.351 to 0.510. In the same experiment, the ratio of hydrohydrazination products was
found to be 0.442 i 0.339 (99% confidence level, 1125), with the range from 0.236 to

0.750. The ranges were fairly large; however, the product ratios are sensitive to the

118

structure of the ligand present on the catalyst. For example, anti-Markovnikov product

has been obtained exclusively when 28 is used instead of l for the above reaction.

Although the errors are relatively large, the mean values are very close. This suggests
that the ratio of different isomers is nearly the same for both iminohydrazination and
hydrohydrazination reactions. The similar ratios are associated with the regiochemistry
prior to the protonolysis or 1,1—insertion, i.e., associated with the [2 + 2]-cycloaddition
and/or alkyne coordination step. This is consistent with the recent assertion by the Beller

group that titanium hydroamination regioselectivities correlate with the alkyne

. . . . . . 42 . . . .
coordination regioselectiVities. The eqUilibrium between the two azatitanacyclobutenes

forms the regioisomers for both iminohydrazination and hydrohydrazination products.
Therefore, the mean values are remarkably close. The relative rates Of trapping for the
azatitanacyclobutene by proton (protonolysis) or tert-butylisonitrile (1,1-insertion of
isonitrile) are different leading to the slight difference in the ratios of the products
(hydrohydrazination vs iminohydrazination). Changing the ancillary ligand set on
titanium greatly affects the product ratios. In particular, the anti-Markovnikov product is
obtained exclusively when 28 is used instead of 1. But the iminohydrazination and
hydrohydrazination products are obtained in the same ratio as obtained for l (the
observed ratios between 3-component coupling product and hydrohydrazinated product
are 4:1 for 1, and 3.2:1 for 28). This suggests that the [2 + 2]-cycloaddition step is
dramatically affected by changing the ancillary ligand set but relative rates of

protonolysis or 1,1-insertion of isonitrile are not affected much.

“9

Table 3.4 Iminohydrazination of phenylacetylene by different catalysts

t

 

 

 

 

Bu HN N’NMez
Ph : H MeZN— Nx / )L
1 ph Me Markovnikov
10% catalyst Ph ' product
MezNNHz = + A + A
+ toluene, 100 °C Me N
CN_But 16 h ButHN 2 ‘N
Me2N-N \ / anti-Markovnikov
H product
Ph Ph
8 B'
3-component Hydrohydrazinated
coupling product product
Catalyst [A] / [B] [A'] / [B']
1 0.453 1- 0.117 0.442 t 0.339
36 0.558 0.364
38 0.478 0.238

 

We also note that the observed ratios of the regioisomers for iminohydrazination and

hydrohydrazination products using 36 as catalyst are 0.558 and 0.364 respectively (Table

3.4). This is comparable to the ratios obtained using 1 (Table 3.4). This suggests that 36

is also an effective catalyst for this iminohydrazination reaction.

The structure of 36 reveals that it has one dap ligand attached to the titanium center.

So the actual catalytically active species might involve only one dap ligand on titanium.

To verify this, a new molecule Ti(dap)(NMe2)3 (38) was synthesized by adding Lidap to

Ti(NMe2)3CI (Equation 3.13). The catalytic activity of 38 was compared with 1 by

comparing the ratios of the regioisomers for the reactions shown in Table 3.4. The ratios

for the iminohydrazination and hydrohydrazination products are found to be 0.478 and

120

0.238. These are again comparable to the product ratios obtained for l as the precatalyst.

Therefore, the active species might involve a titanium center carrying only one dap

hgand.

_ ether _
Ti((NMe2)3Cl + Lidap = Ti(daprMezla (3.13)
cold-RT, 12 h 38

80%

 

3.4 Applications of the Iminiohydrazination reaction towards the synthesis of
pyrazoles

3.4.1 Background information

The products of iminohydrazination reactions are basically a,B-unsaturated [3-
aminohydrazones. Barluenga and co-workers have shown the formation of different

heterocycles starting from 4-amino-1-azabutadienes (in other words, a,[3-unsaturated [3-

. . . . 43-45
aminOimines) as shown in Scheme 3.4.

Scheme 3.4 Synthesis of pyrazole from 4-amino-1-azabutadienes

 

R N“ , 3 R3
+ pyrldine = R\/E\NHR1 _____ H{FNR1
-NH4C' 4 \ 5 4 \ 5

H2NNHR5-HCI - _

 

 

 

We have been exploring similar reactions with our iminohydrazination products.

3.4.2 Results and Discussion

The isolated 3-component coupling product from iminohydrazination was allowed to

react with N2H4-HZO at 150 °C for 24 h in pyridine (Equations 3.14 and 3.15). In these

cases only one pyrazole product was obtained in good to excellent yield.

 

 

NMez
Bun 1'4 pyridine H
/ N’
+ N H -H o 1 | (3.14)
KNHBUIL 2 4 2 150°C, 24h Bunk)
30 96% 39
NMe
l 2 H
,N pyridine N’N
t + N H -H o > | (3.15)
ph \ NHBU 2 4 2 150°C, 24h /
34 70% Ph
40

To investigate the mechanism of this reaction, we performed the reaction of
compound 30 with phenylhydrazine where there is the possibility of forming two
different pyrazoles. Both the titanium-catalyzed reaction and the cyclization with

phenylhydrazine were carried out in a one-pot procedure (Scheme 3.5). Two different

isomers were obtained in 10:1 ratio (usmg Bu NC) under the speCified reaction

conditions.

Scheme 3.5 Synthesis of N-phenyl-S-n-butylpyrazole and N-phenyl-B-n-butylpyrazole

n

 

H : Bu [TIMeZ

+

n
10% Ti(dap)2(NMe2)2 (1) BU\:N/
Me NNH e
E 2 toluene, 100 °C, 16 h \ NHR

 

RNC — RNH2 PhNHNH2
— MezNNHz pyridine, 150 °C, 24 h

 

ll

n
MB” U
EU"
41 42
- t .
R - Bu , 10.1
Cy = cyclohexyl R = Cy, 5.1

Mechanistically, the formation of the products can be understood by considering four

different modes of attack of the two nitrogen atoms on phenylhydrazine (Scheme 3.6)

However, among these four possibilities, pathways (a), and (c) are more likely from the

steric point as well as the nucleophilic attack by phenylhydrazine can be considered as

1.4-addition to a,B-unsaturated imine.

Scheme 3.6 Possible mechanistic pathways for the pyrazole formation

 

 

 

 

 

(a)
NMe
n ' 2 W32 t
BUf: Bu NH — Bu NH2>
t
\ NHBU I fNBut
30 30
+
H )
Ph’ ‘NH2
Me N NMez
80,7211?H 3“" ('1‘ H Pb M NNH
l :uHPh . ifihHPh _ {N’N fNHNMez ' 92 2;
LN \ NH l<9<laun
13h
,N
N
MBU"
41
n n
BU EN BU N‘NHPh —M62NNH2 Bu I N\.N.th
\ NHBut ————-> ”W l " ' J
MezN t (I t
30 (N80 NBu
H
+
H2N, ,Ph [3h
fl H\ h —ButNH2 N’N

 

 

 

 

 

 

 

 

 

80" /N Bu" ,l‘H EU | NNHZ —Bu’NH2;
LNHBU’ | fNBu’ ‘1 Mph
30 H #1 (NHBut
Ph’” H2
Bun (EMGZ Ph 7" F“
9"?“2 ; \N’N) (NlealMez ‘ MeZNNH; NI":
\ N‘Ph \ 3” Bu"
42
(d) n 'flMez ,lsh n lfh
Bu 5N A Bun N‘NH —M62NNH£ Bu N‘NHZ
KNHBut , “181% " 2 7 1.}.
3° MeZN {NB t (lLlBut
+ H’ U
H2N,N,Ph
H
Bun N?" t 13h
_ \ —Bu NH2 _ N’N n
' I ElfH ' U—Bu
(NHBut 41

From the observed ratio of the products in Scheme 3.5, it is clear that the major
product has been obtained following pathway (a) under the conditions of the reaction. In

(a), phenylhydrazine attacks on the carbon atom coming from the isonitrile group as

126

opposed to the other carbon atom adjacent to dimethylhydrazine in the 3-component

coupling product (pathway (b)).

We further wanted to explore the effect of isonitrile sterics on the mode of attack
shown in (a). For this, we carried out reactions with two different isonitriles as shown in
Scheme 3.5. Since a cyclohexyl group is smaller in size than a tert-butyl group, the ratio
of the pyrazole products should change if steric factor is important. From the
experimental data, we observed similar product ratios for both of them. This indicates

that there is no obvious effect of isonitrile sterics in the cyclization step.

We also carried out experiments to discover how the electronics of the substituents
on the phenyl ring affects the regioselectivity. For this, three different para-substituted

phenylhydrazines were used, and the ratio of the corresponding pyrazole products was

observed by 1H NMR spectroscopy (Table 3.5).

Table 3.5 Effect ofp-substituents on arylhydrazine on pyrazole formation

_ n
H _ Bu HMez

n
+ 10% Ti(dap)2(NMe2)2 (1) Sufi
Me NNH >
2 2 toluene, 100 °C, 16 h \ NHBu‘
+ 30

ButNC

 

 

pyridine, 150 °C, 24 h

 

 

 

NHNH2
ll
1 X
’N ’N
N n N
+
MB“ ”U
Bu
azb
Entry X Ratio (azb)
l H 10:]
2 OMe 2:1
3 F 4.5:]
4 CN 1:6

 

From the data shown in Table 3.5, it is observed that isomer a is preferred when X =
H. This can be explained following pathway (a) in Scheme 3.6. However, when X =
OMe, substantial amount of isomer b (minor) is produced along with a (major). This can

be explained following pathway (c) in Scheme 3.6, which includes the attack by 01-

nitrogen atom of arylhydrazine. This can happen due to the n-donor ability of OMe
group. So the observed ratio of the products azb is 2: 1. When X = F, it has both electron
withdrawing effect and it-donor ability. This makes (it-nitrogen atom sufficiently
nucleophilic so that isomer b can be formed following pathway (c). But the selectivity is
more than the case when X = OMe since F also has electron withdrawing effect, which
produces isomer a according to pathway (a). When X = CN, which has both electron
withdrawing effect and n—accepting ability, formation of isomer b is favored. This can be
due to the attack by (ii-nitrogen atom of arylhydrazine following pathway (0). In this case,
iii-nitrogen is preferred over B-nitrogen in arylhydrazine because the hydrogen on a-

nitrogen is more acidic due to the presence of p-CN group.

3.5 Multicomponent Coupling Reactions of alkynes, monosubstituted hydrazines,
and isonitriles

After the success of using a tetradentate ligand (Hzenp, 4) on titanium(IV) for

hydrohydrazination of alkynes with monosubstituted hydrazines (discussed in Chapter 2),
we have attempted application of this ligand framework towards 3-component couplings
with isonitriles. Unfortunately, multicomponent coupling reactions of alkynes,

monosubstituted hydrazines, and isonitriles did not produce the expected 3—component

coupling product using Ti(enp)(NMe2)2 (5) as precatalyst. Instead, only

hydrohydrazination products were obtained. Therefore, we have screened other catalysts

for this transformation.

We have observed (Scheme 3.3) that the active species in the iminohydrazination
reaction contains only one dap attached to the metal center. Hence, one dap is
protolytically labile under the reaction conditions. The presence of the tetradentate enp is
possibly inhibiting the formation of species that would be active for 3-component
coupling. The enp ligand on the metal center forms a stable five-membered metallacycle

with titanium, and it may be difficult to remove one of the pyrrolyl groups. So, we

decided to investigate the effect of the Hdap3-mes ligand on titanium(IV), and its catalytic
efficiency for the 3-component coupling reaction with monosubstituted hydrazines.

Hdap}mes (43) was synthesized as shown in Scheme 3.7. At first, Boc-pyrrole was

borylated at the 3- position using Smith borylation,46 followed by Suzuki coupling47 in

the presence of catalytic Pd(PPh3)4 (Boc is Iert-butyloxycarbonyl). The next step was

130

removal of BOC-group by heating the reaction mixture at 100 °C for 24 h in BunOH and

excess K3PO4°nHzO (Scheme 3.7). All of these steps were carried out in a single pot.

The final product, 3-mesitylpyrrole (43), was isolated in 85% overall yield. An ORTEP
representation of the X-ray crystal structure of 43 is shown in Figure 3.10. The next step

involved Mannich reaction with formaldehyde and dimethylamine hydrochloride in

ethanol at 45 °C. The final product, Hdap}mes (44) was isolated in 89% yield.

Scheme 3.7 Synthesis of 3-mesitylpyrrole (43)

 

 

 

 

1-5 mol% [|r(OMe)(COD)]2 2.5 mol% Pd(PPh3)4 Me
0 / N\ N" BOC
poo 3 m°'/° _ \ / soc 1 equiv. Me Br N’
N t t N | /
BU 3” Me
U = Q ; Me
1.5 equiv. HBpin B in 5 equiv. K3PO4-nH20 Me
pentane. 60 °C, 24 h " DME, 100 °C, 24 h
Me
ii
1‘1 1.1 equiv. HZC=O Me2N N
N
BunOH, 100°C, 24 h l / MezNH-HCI I /
> 1 Me
1.2 equiV- K31394111120 Me ethanol, 45 °C, 24 h Me
Me
Me
Me
43 44
85% 39%

I31

Figure 3.10 ORTEP representation of 3-mesity1pyrrole (43).

rfl/ C(13l
v)

 

.4.

Clill “I

 

In the next step, the precatalyst Ti(dap3-mes)2(NMe2)2 (45) was synthesized by

me

adding two equiv of Hdap} S to Ti(NMe2)4, and the catalyst was isolated in 82% yield

(Equation 3.16).

Me

 

Me
MezN Me NMe2
n ether \\N'l 1|. \\NMe2
Ti(NMe) + 2 1 i"‘ (3.16)
24 i / cold-RT, 12h RIM/l \NMez
Me 82% 2”
Me
”Me
Me
Me 45

Complex 45 was also crystallographically characterized as shown in Figure 3.11. One
of the amido groups has a pyrrolyl group in the trans-position instead of an amine donor
nitrogen as might be expected (donor ability of the ligands are amido > pyrrolyl >

amine). This might be due to the sterically bulky substituents present on the pyrrolyl

group.

Figure 3.11 ORTEP representation of Ti(dap3-mes)2(NMe2)2 (45). Selected bond
lengths(A) and bond angles(°) are: Ti(1)—N(5) = 1.9076(15), Ti(l) -N(6) = 1.9156(16),
Ti(1)—N(1) = 2.0548(15), Ti(1)—N(3) = 2.1035(15), Ti(l)—N(4) = 2.4276(15), Ti(1)—N(2)
= 2.5510(16), N(5)—Ti(1)—N(6) = 100.08(7), N(5)—Ti(1)—N(1) = 9333(6), N(6)—Ti(1)—
N(l) = 105.75(6), N(5)—Ti(1)—N(3) = 9326(6), N(6)—Ti(1)—N(3) = 157.45(7), N(1)—
Ti(1)—N(3) = 91.41(6), N(5)-Ti(1)—N(4) = 90.41(6), N(6)—Ti(1)—N(4) = 8915(6), N(1)—
Ti(1)—N(4) = 163.71(6).

‘A
Is

   

Unfortunately, three-component coupling of alkyne with monosubstituted hydrazine
and isonitrile was not generally successful using 45 as the catalyst except for where
phenylacetylene was used as the alkyne. Using phenylacetylene, two different products
were formed; the uncyclized 3-component coupling product and the pyrazole (Equation

3.17). They were obtained in ~ 40% yield as observed by GC/FID. No reaction was

134

observed with l-hexyne or l-phenylpropyne as substrate under the same reaction

 

 

conditions.
Ph : H t Ipn
* 10 mol% 45 Ph\ Bu HN N,N
PhNHNH = -—N + l (3.17)
. t2 toluene, 150 °C, 16h H)“ \\ /<‘ K?
CN-Bu 40% Ph Ph
1:1

However, compound 45 was an active catalyst for hydroamination of l-hexyne with
aniline at 100 °C in 2—3 h. In addition, 45 was active for hydrohydrazination of 1-hexyne
with 1,1-dimethylhydrazine under the same conditions. Three component coupling
reactions carried out with both aniline and 1,1-dimethylhydrazine resulted in only 10%
multicomponent coupling product. In these cases, the major products were the imine and

hydrazone, respectively.

135

3.6 Concluding Remarks

Alkynes have been successfully transformed into [LU-unsaturated [l-aminohydrazones
through multicomponent coupling of alkyne, 1,1—disubstituted hydrazine, and isonitrile.
This reaction has been effectively catalyzed by titanium pyrrolyl-based catalysts. The
reaction is quite general in the sense that it tolerates both terminal and internal alkynes
with aliphatic and aromatic isonitriles. Mechanistically, the reaction involves a titanium
hydrazido(2—) complex 36 as the intermediate (Scheme 3.3). The reaction also involves
the formation of a titanium dinuclear species 37, which is not kinetically competent for
the iminohydrazination reaction. Consequently, the catalyst concentration may be
constantly changing during these catalyses. However, with the available data from the
kinetic experiments, the mechanism can be envisioned as follows: the formation of the
product involves a hydrazido(2—) intermediate, followed by [2 + 2]-cycloaddition of
alkyne to form an azatitanacyclobutene. This cycloaddition is followed by 1,1-insertion
of isonitrile forming a new Ti—C bond. The five-membered metallacycle then undergoes
intramolecular proton transfer to form the isolable intermediate 36. Compound 36 finally
undergoes protonolysis by hydrazine forming the 3-component coupling product
(Scheme 3.3). The reaction has also been efficiently applied to the synthesis of different

pyrazoles by adding hydrazine to the 3-component coupling product.

136

3.7 Experimental

General Considerations

All manipulations of air sensitive compounds were carried out in an MBraun drybox
under a purified nitrogen atmosphere. All the solvents were purified according to the
standard procedure. Hydrazines were purchased from Aldrich Chemical Company and

dried by distillation from KOH under dry nitrogen. Alkynes were distilled under dry

. 4 2
nitrogen over CaO. Ti(NMe2)4,48 TiCl(NMe2)3, 9 Hdap,25 Hbap, 7 tert-butyl
. . . 50 . . . 51 . .
isonitrile, and 2,6-xylyl isonitrile were prepared usmg the literature procedures.

Lidap was prepared by addition of 1.1 equivalents of LiBun to a toluene solution of

Hdap; the Lidap was collected by filtration and washed with pentane to afford the
colorless product. Cyclohexyl isonitrile was purchased from Aldrich Chemical Company

and distilled under dry nitrogen prior to use. Deuterated solvents were dried over purple

sodium benzophenone ketyl (C6D6) or phosphOiic anhydride (CDCl3) and distilled under

3 .

nitrogen. 1H and I C spectra were recorded on Inova-300 or VXR—SOO spectrometers. 1H

and 13C assignments were confirmed when necessary with the use of two-dimensional
l 1 l3 1 . . .

H— H and C— H correlation NMR experiments. All spectra were referenced internally

. . 1 l3 .
to res1dual protiosolvent ( H) or solvent ( C) resonances. Many common coupling

constants are not listed. Chemical shifts are quoted in ppm and coupling constants in Hz.

137

Synthesis and characterization of Ti(bap)(NMe2)3 (28)

NMe
MezN ( Ti 2’3

N' \NMez
' /

Under an atmosphere of dry nitrogen, a solution of Ti(NMe2)4 (2.000 g, 8.9 mmol) in

ether (20 mL) was frozen in a liquid nitrogen cooled cold well. The solution was allowed
to warm enough to be stirred. Then, a cold solution of Hbap (1.610 g, 8.900 mmol) in 10
mL ether was added to the above solution dropwise over a period of 20 min. It was
allowed to warm up to room temperature and stir overnight. The volatiles were removed

under vacuum. The solid was purified by crystallization as orange-red crystals from

pentane (2.950 g, 8.200 mmol) in 92% yield. 1H NMR (299.8 MHz, CDC13): 6.34 (s, 2
H, 3H—pyrrole), 3.48 (s, 4 H, CH2), 3.13 (s, 12 H, CH2N(CH3)2), 2.07 (s,‘ 18 H,

N(CH3)2). l3c1111} NMR (75.4 MHz, CDC13): 137.9, 106.9, 60.0, 47.1, 45.8. Elemental

analysis; Experimental (Calc.), C: 53.19 (53.33). H: 10.09 (10.07). N: 22.82 (23.32). M.p.

118-120 °C.

138

Synthesis of compound 30
,C(CH3)3

MezN—N\ /

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (6000 UL), Ti(dap)2(NMe2)2 (0.458 g, 1.200 mmol), 1,1-dimethylhydrazine (910

EL, 12 mmol), l-hexyne (1399 BL, 12 mmol), and tert-butyl isocyanide (1355 BL, 12
mmol). The tube was sealed with a Teflon cap and heated at 100 °C for 16 h. The solvent

was removed under vacuum. The product was isolated by distillation under vacuum (~65

°C, 0.65 torr) in 63% yield (1.702 g, 7.564 mmol) as red oil. 1H. NMR (299.8 MHz,
CDCI3): 9.82 (br s, 1 H, NHC), 6.88 (d, l H, JHH = 8.1 Hz, HNCH), 4.68 (d, l H, JHH =
8.1 Hz, HNCHCH), 2.71 (m, 8 H, N(CH3)2 and N=CCH2), 1.77 (m, 2 H, N=CCH2CH2),
1.64 (m, 2 H, N=CCH2CH2CH2), 1.52 (s, 9 H, CCH3), 1.17 (t, 3 H, JHH = 8.0 Hz,

C(CH3)3). 13C{ 111} NMR (75.4 MHz, CDC13): 171.5, 139.6, 89.5, 51.5, 48.9, 47.5, 31.2,

30.4, 23.1, 13.9. Elemental analysis; Experimental (Calc.), C: 69.41 (69.33). H: 12.35

(12.00). N: 18.85 (18.67). MS (EI) m/z = 225(M+).

139

Synthesis of compound 31

Q

HN
M __
€2N N\ /

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (6000 UL), Ti(dap)2(NMe2)2 (0.457 g, 1.200 mmol), 1,1-dimethylhydrazine (910

uL, 12 mmol), l—hexyne (1399 UL, 12 mmol), and cyclohexyl isocyanide (1790 11L,
14.400 mmol). The tube was sealed with a Teflon cap and heated at 100 °C for 16 h. The

solvent was removed under vacuum. The product was isolated by distillation under

vacuum (~110 0C, 0.65 torr) in 73% yield (2.205 g, 8.785 mmol) as brown oil. 1H NMR
(299.8 MHz, CDC13): 9.61 (br s, 1 H, NH), 6.74 (d, l H, JHH = 8.1 Hz, HNCH), 4.61 (d,
1 H, 11111 = 8.1 Hz, HNCHCH), 2.68 (m, 8 H, N(CH3)2 and N=CCH2), 2.09-1.93 (m, 11
H, cyclohexyl), 1.73 (m, 2 H, N=CCH2CH2), 1.57 (m, 2 H, N=CCH2CH2CH2), 1.14 (t, 3

H, JHH = 7.1 Hz, CH3). 13C{1H} NMR (75.4 MHz, coc13): 171.9, 142.5, 89.9, 56.0,

49.8, 47.9, 34.8, 31.5, 26.2, 24.9, 23.0, 13.9. Elemental analysis; Experimental (Calc.), C:

71.71 (71.71). H: 11.96 (11.55). N: 16.80 (16.73). MS (EI) m/z = 251(M+).

140

Synthesis of compound 32

Me

HN Me
M92N*N\ /

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (4500 UL), Ti(dap)2(NMe2)2 (0.344 g, 0.900 mmol), 1,1-dimethylhydrazine (1024

11L, 13.500 mmol), 1-phenylpropyne (1078 11L, 9 mmol), and xylyl isocyanide (1.769 g,
13.500 mmol). The tube was sealed with a Teflon cap and heated at 130 °C for 43 h. The
volatiles were removed under vacuum. The product was then isolated by column
chromatography on Florisil. The impurities were removed as the first fraction using 1:]

pentane:ethyl acetate mixture. The product was then isolated with pure ethyl acetate in

14% yield (0.401 g, 1.306 mmol) as a dark brown viscous oil. 1H NMR (299.8 MHz,
CDC13): 11.31 (br s, 1 H, NH), 7.35 — 6.69 (m, 8 H, Ph), 6.82 (d, 1 H, JHH = 7.3 Hz,

HNCH), 2.66 (s, 6 H, N(CH3)2), 2.43 (s, 6 H, 2,6-(CH3)2C6H3), 2.23 (s, 3 H, N=CCH3).

13C{1H} NMR (75.4 MHz, CDC13): 166.3, 142.7, 143.0, 142.0, 141.8, 131.0, 129.0,

128.1, 126.8, 125.9, 123.9, 108.3, 48.2, 19.5, 17.9. Elemental analysis; Experimental

(Calc.), C: 77.88 (78.17). H: 8.33 (8.14). N: 13.49 (13.68). MS (EI) m/z = 307(M+).

Synthesis of compound 33

141

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (4500 UL), Ti(dap)2(NMe2)2 (0.344 g, 0.900 mmol), l-methyl-l—phenylhydrazine

(1059 11L, 9 mmol), 1-hexyne (1119 UL, 9 mmol), and tert-butyl isocyanide (1018 1.1L, 9
mmol). The tube was sealed with a Teflon cap and heated at 100 °C for 13 h. The solvent

was removed under vacuum. The product was isolated by distillation under vacuum

(~110 °C, 0.65 torr) in 27% yield (0.693 g, 2.414 mmol) as dark brown oil. 1H NMR
(299.8 MHz, CDC13): 9.69 (br s, 1 H, NH), 7.27-6.83 (m, 5 H, Ph), 6.93 (m, 1 H,
HNCH), 4.57 (d, l H, JHH =8.l Hz, HNCHCH), 3.11 (s, 3 H, N(CH3)2), 2.36 (t, 2 H,
JHH = 7.7 Hz , N=CCH2), 1.50 (m, 2 H, N=CCH2CH2), 1.39 (m, 2 H,
N=CCH2CH2CH2), 1.29 (s, 9 H, CH3), 0.89 (t, 3 H, JHH = 7.2 Hz, C(CH3)3). 13C{ 1H}

NMR (75.4 MHz, CDCI3): 176.3, 152.2, 140.9, 128.5, 118.0, 113.9, 89.1, 51.0, 42.8,

32.0, 30.3, 30.1, 22.8, 1.3.8. Elemental analysis; Experimental (Calc.), C: 75.29 (75.26).

H: 10.49 (10.10). N: 14.72 (14.63). MS (EI) m/z = 287(M+).

Synthesis of compound 34

142

C(CH3)3

I
l

NI
M82N_N\ /

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (4900 UL), Ti(bap)(NMe2)3 (0.353 g, 0.980 mmol), 1,1—dimethylhydrazine (743

uL, 9.800 mmol), phenylacetylene (1075 UL, 9.800 mmol), and tert-butyl isocyanide
(1107 11L, 9.800 mmol). The tube was sealed with a Teflon cap and heated at 100 °C for

16 h. The solvent was removed under vacuum. The product was isolated by distillation

under vacuum (~125 °C, 0.65 torr) in 43% yield (1.030 g, 34.204 mmol) as a red oil. 1H
NMR (299.8 MHz, CDCl3): 9.03 (br d, 1 H, 11111 = 13.0 Hz, NH), 7.65 (s, l H, N=CCH),
7.40—7.15 (m, 5 H, Ph), 6.89 (d, 1 H, JHH = 2.3 Hz, HNCH), 2.83 (s, 6 H, N(CH3)2),

1.36 (s, 9 H, C(CH3)3). 13C{1H} NMR (75.4 MHz, CDC13): 143.0, 142.0, 136.0, 128.5,
125.0, 124.0, 102.9, 50.9, 42.0, 30.0. Elemental analysis; Experimental (Calc.), C: 73.58

(73.47). H: 9.26 (9.39). N: 17.05 (17.14). MS (EI) m/z = 245(M+).

143

Synthesis of compound 35

Me

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

toluene (60001]L), Ti(dap)2(NMe2)2 (0.4319 g, 1.200 mmol), 1,1-dimethylhydrazine (910

11L, 12 mmol), 1-hexyne (1399 UL, 12 mmol), and xylyl isocyanide (1.573 g, 12 mmol).
The tube was sealed with a Teflon cap and heated at 100 °C for 16 h. The volatiles were
removed under vacuum. The product was then isolated by column chromatography on
Florisil. The impurities were removed as the first fraction using 1:1

dichloromethane:ethyl acetate mixture. The product was then isolated with ethyl acetate

as the eluent in 12% yield (0.401 g, 1.469 mmol) as a viscous oil. 1H NMR (299.8 MHz,

CDC13): 10.89 (br s, 1 H, NH), 7.15 - 6.85 (m, 3 H, 0, m-CH), 6.78 (d, 2 H, JHH = 7.8
Hz, HNCH), 4.62 (d, 1 H, JHH = 8.0 Hz, N=CCH), 2.58 (m, 8 H, N(CH3)2 and
N=CCH2), 2.38 (s, 6 H, 2,6-(CH3)2C6H3), 1.59 (m, 2 H, N=CCH2CH2), 1.41 (m, 2 H,
N=CCH2CH2CH2), 0.99 (t, 3 H, 13):] = 7.3 Hz, CHZCH3). 13C{1H} NMR (75.4 MHz,

CDC13): 170.4, 143.1, 141.8, 131.7, 128.7, 128.6, 124.1, 1.22.1, 117.9, 92.0, 48.8, 46.6,

31.4, 23.0, 19.3, 14.0. High Resolution MS (EI) m/z = 273.2200, calc. 2 273.2205.

144

Synthesis of Ti(NNMez)(daP)[N(But)CHCHC(Bun)N(NMe2)-k2N] (36)

 

All the manipulations were done inside the glove-box filled with nitrogen. 1,1-

MeZNNHz (91 11L, 1.2 mmol) was added to Ti(dap)2(NMe2)2 (0.4538 g, 1.2 mmol)

dissolved in 600 11L of toluene in a vial. It was then cooled in the cold well filled with

liquid nitrogen. To this were added cold solutions of 1-hexyne (0.1 g, 1.2 mmol) and

I
Bu NC (136 11L, 1.2 mmol). It was then allowed to warm up to the room temperature and

stir for 12 h. It was then kept at —35 °C for overnight. The solvent was then pumped
down and the reddish-brown residue was crystallized from pentane as orange-red colored

plate-shaped crystals in 94% yield (0.256 g, 0.565 mmol) with respect to limiting

hydrazine. 1H NMR (499.7 MHz, c6136): 7.09 (d, 1 H, i), 6.73 (t, 1 H, JHH = 2.1 Hz, r),
6.59 (t,1 H, JHH = 2.3 Hz, q), 6.47 (m, 1 H, p), 4.67 (d, 1 H, JHH = 12.4 Hz, 11), 4.56 (d,

1 H, JHHZ 7.4 Hz, i), 3.34 (d, 2 H, JHH = 12.4 Hz, 11), 3.09 (m, 1 H, d), 2.87 (br s, 6 H,
a), 2.60 (br s, 3 H, 1 or m), 2.56 (s, 6 H, b), 2.29 (m, 1 H, d), 1.74 (br s, 3 H, l or m), 1.51

(m, 2 H, e), 1.31 (s. 9 H, k), 1.29 (m, 2 H, 1), 0.89 (t, 3 H, JHH= 7.3 Hz, g). l3C{'H}

NMR (125.7 MHZ. C6D6): 166.7, 146.9, 136.2, 126.8, 107.1, 104.1, 93.2. 63.3, 56.9,

145

50.1, 49.7, 49.1, 33.7, 32.0, 31.7, 31.5, 23.3, 14.2. Elemental analysis; Experimental

(Calc.), C: 57.83 (58.27). H: 9.25 (9.56). N: 21.36 (21.62). M.p. decomp. 230 °C.

Structural details: (Monoclinic, P2(1)/c, Formula: C22H43N7Ti, a = 9.180(1), b =

19.161(3), c = 15.043(2), 13 = 102.598(3)°, Z = 4, Dcajc = 1.167 g/mL, p. = 0.353 mm_],
F(000) = 984, 0 range = 1.75 to 23.33°, total ref = 22066, unique ref = 3737, parameters

= 272, (101‘ = 1.012, s = 0.020(2), largest peak and hole = 0.414 and —0.398 eA_3, R (I >

26(1)) = 0.0436, sz (1 > 26(1)) = 0.1040.)

146

Synthesis and characterization of Ti2(dap)3(NHNMe2)(NNMe2)2 (37)

C} I p a
r Me (1
s 0 \Me ,NMe

All the manipulations were done inside a nitrogen filled glove-box. In a vial,

Ti(dap)2(NMez)2 (0.200 g, 0.500 mmol) was dissolved in toluene (250 pL). It was then

cooled in a liquid nitrogen-cooled cold we11. To this solution was added 1,1-Me2NNH2

(76 1.11., 1.000 mmol). Then, the solution was allowed to warm up to room temperature
and stir for 1 h. The solution was kept in the refrigerator at —35 °C overnight. The
volatiles were removed in vacuo, and the yellow-brown residue was crystallized from a

1:1 dichloromethane2pentane to obtain 37 as yellow plates in 61% yield (0.195 g, 0.305

mmol). 1H NMR (499.7 MHz, C6D6): 7.68 (br, 1 H, c), 6.89 (br, 1 H, r or x), 6.56 (t, l

H, JHH = 2.7 Hz, q or w), 6.40 (t, 2 H, JHH = 2.5 Hz, q or w and r or x), 6.34 (br, 1 H, p
or v), 6.22 (br, 1 H,j), 6.17 (t, l H, JHH = 2.6 Hz, 1), 6.08 (br, 1 H, p or v), 5.77 (br, 1 H,
h), 3.99 (d, 1 H, JHH = 13.8 Hz, f), 3.87 (d, 1 H, JHH = 13.8 Hz, n or t), 3.78 (d, 1 H,
JHH = 13.4 Hz, 11 or t), 3.57 (d, 1 H, JHH = 13.4 Hz, 11 or t), 3.52 (d, 1 H, n or t, JHH =

13.8), 3.12 (d, 1 H, f, JHH = 13.8), 2.95 (br, 3 H, a or b or k or I), 2.85 (br, 6 H, m or s),

2.68 (br, 3 H, a or b or k or I), 2.42 (br, 6 H, d), 2.32 (br, 3 H, a or b or k or 1), 2.29 (br, 3

147

H, a or b or k or 1), 2.26 (br, 6 H, m or s), 1.86 (br, 6 H, e). 13C{1H} NMR (125.7 MHz,

C6D6): 137.2, 136.1, 133.5, 130.6, 129.5, 108.0, 107.3, 106.7, 102.1, 101.8, 101.4, 65.5,

63.0, 62.9, 54.4, 54.3, 51.0, 50.6, 50.3, 49.8, 49.4. Elemental analysis; Experimental

(Calc.), C: 50.93 (50.64). H: 8.48 (8.12). N: 26.07 (26.25). M.p. decomp. 230 °C.

148

Synthesis and characterization of Ti(dap)(NMe2)3 (38)

Under an atmosphere of dry nitrogen, Ti(NMe2)3(Cl) (0.200 g, 0.9 mmol) was

dissolved in 15 mL ether in a filter flask. Lidap (0.121 g, 0.9 mmol) was dissolved in 5

mL ether in a vial. Both of them were cooled in the cold well. Then Lidap solution was

added to the solution of Ti(NMe2)3Cl and allowed to warm up to the room temperature

and stir overnight. Then it was filtered, and the solvent was pumped down. The product

was isolated by crystallization from 1:1 ether: pentane as reddish-brown crystals in 80%

yield (0.218 g, 0.7 mmol). 1H NMR (299.8 MHz, CDCI3): 6.80 (q, 1 H, S-pyrrolyl), 6.02
(t, 1 H, JHH = 2.6 Hz, 4H-pyrrolyl), 5.82 (m, 1 H, 3H—pyrrolyl), 3.51 (s, 2 H, CH2), 3.22

(s, 18 H, amido CH3), 2.36 (s, 6 H, amine CH3). l3C{1H} NMR (75.4 MHz, CDC13):

142.9, 133.3, 122.0, 107.5, 65.2, 53.3, 51.6. M.p. 148-150 0C.

Attempted reaction of l-hexyne, N,N,NU-trimethylhydrazine, and tert-butylisonitrile
in presence of Ti(dap)2(NMe2)2 (1)

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with
toluene (300 11L), Ti(dap)2(NMe2)2 (1) (0.023 g, 0.06 mmol), N,N,ND-tiimethylhydrazine
(0.044 g, 0.6 mmol), l—hexyne (0.050 g, 0.6 mmol), and tert-butyl isocyanide (68 UL, 0.6
mmol). The tube was sealed with a Teflon cap and heated at 100 °C for 16 h. The residue

was analyzed with GC—FID. Only starting materials were observed, and no product was

detected under these reaction conditions.

149

Synthesis of 3-n-butylpyrazole (39)

A pressure tube was loaded with 30 (0.100 g, 0.4 mmol), hydrazine (0.0156 g, 0.4

mmol), and pyridine (1 mL). The solution was heated at 150 °C for 24 h. The tube was

allowed to cool to room temperature. CH2C12 (25 mL) was added, and the solution was
extracted with water. The organic layer was dried over Na2SO4, filtered, and dried under

vacuum. This yielded the pure product52 in 96% (0.0476 g, 0.380 mmol) yield. lH NMR

(499.7 MHz. coc13): 8.60 (br s, i H, NH), 7.46 (d, 1 H, JHH= 2.0 Hz, NCHC), 6.06 (d,
1 H, JHH = 1.9 Hz, NC(Bun)CH), 2.66 (t, 2 H, JHH = 7.6 Hz, NCCHZ), 1.62 (m, 2 H,
NCCHZCH2). 1.35 (m, 2 H, CHZCH3). 0.91 (t. 3 H, JHH = 7.4 Hz, CH3). 13c {'H}

NMR (125.7 MHz, CDC13): 147.9, 135.1, 103.4, 31.5, 26.3, 22.3, 13.8. MS (EI) m/z =

124 (M+).

150

Synthesis of 4-phenylpyrazole (40)

N’N

A pressure tube was loaded with 34 (0.05 g. 0.200 mmol), hydrazine (0.0064 g, 0.200

mmol), and pyridine (1 mL). The mixture was heated at 150 °C for 24 h. The solution

was allowed to cool to room temperature. CH2C12 (25 mL) was added, and the solution

was extracted with water. The organic layer was dried over NazSO4, filtered, and dried

under vacuum. This resulted in a white solid. The product was isolated by crystallization

from 3:1 methanolzethylacetate at 5 °C. The product53 was isolated as colorless crystals

in 70% (0.02 g, 0.14 mmol) yield. ]H NMR (499.7 MHz, DMSO): 12.9 (br s, 1 H, NH),

7.65 (m, 2 H, ortho-CH), 7.39 (tt, 2 H, JHH = 1.21, 7.55 Hz, meta-CH), 7.22 (tt, 1 H,
JHH = 1.20, 7.35 Hz. para-CH). '3c {1H} NMR (125.7 MHz, CDC13): 133.9, 129.7,

126.7, 126.0, 122.1. MS (E1) m/z = 144 (M+). M.p. 230-232 °C.

151

Synthesis of 5-n-butyl-l-phenylpyrazole (41) and 3-n-butyl-1-phenylpyrazole (42)

/ I /
41 42

Inside a glove box, a pressure tube was loaded with Ti(dap)2(NMe2)2 (0.2326 g,

0.609 mmol), MezNNHg (462 uL, 6.09 mmol), l-hexyne (699 uL, 6.09 mmol), tert-

butylisonitrile (688 11L, 6.09 mmol), and toluene (610 11L). The tube was taken outside

the box and heated at 100 °C for 16 h. The volatiles were removed under vacuum. This

resulted in a dark brown semisolid. To this solid was added PhNHNH2 (60 11L, 6.09

mmol) in pyridine (2 mL). The solution was heated at 150 °C for 24 h. The solution was

then allowed to cool to room temperature, and the volatiles were removed under vacuum.

This resulted in a dark brown semisolid which was dissolved in CH2C12 (30 mL) and

extracted with water (2X25 mL). The organic layer was collected, dried over NazSO4,

and filtered. The volatiles were removed from the filtrate under vacuum. This resulted in

. . 1 .
a brown mass, which was characterized by H NMR spectroscopy. This showed that the

products were formed in 10:1 ratio (41:42). The products were then subjected to column
chromatography on alumina using 20% ethyl acetatezhexanes. Compound 41 was isolated
in the first fraction as a red-yellow oil. Compound 42 was isolated in the second fraction

as a dark red oil. The mixture of products was obtained in 64% (0.78 g, 3.9 mmol) overall

isolated yield. Compound 41: 1H NMR (299.8 MHz, coc13): 7.57 (d, l H, JHH = 1.7

Hz, 3H—pyrazole), 7.56-7.36 (m, 5 H, Ph), 6.19 (td, l H, JHH = 0.7, 1.7 Hz, 4H-
pyrazole), 2.63 (t, 2 H, JHH = 7.6 Hz, NCCHZ), 1.53 (m, 2 H, NCCHZCHz), 1.29 (m, 2
H, CHZCH3), 0.85 (t, 3 H, JHH = 7.3 Hz). 13C {'H} NMR (75.4 MHz, CDC13): 143.8,
140.1, 139.8. 129.0, 127.8, 125.4, 105.3, 30.9, 25.9, 22.3, 13.7. MS (EI) m/z = 200 (M+).

Compound 42: IH NMR (299.8 MHz, CDC13): 7.80 (d, 1 H, JHH = 2.5 Hz, 5H-
pyrazole), 7.64 (d, 2 H, JHH = 8.2 Hz, o-CH-phenyl), 7.47 (t, 2 H, JHH = 7.6 Hz, m-
CH—phenyl), 7.23 (t, 1 H, JHH = 7.0 Hz, p-CH-phenyl). l3C {1H} NMR (75.4 MHz,

CDC13): 155.4, 129.3, 127.2, 125.9, 125.6, 118.9, 106.4, 31.8, 28.1, 22.5, 13.9. MS (EI)

m/z = 200 (M+).

153

Synthesis of 3-mesity1pyrrole (43)

\2I

Me

Me

Inside a glove box, a Schlenk tube (100 mL) was loaded with [lr(OMe)(COD)]2,

(0.1786 g, 0.264 mmol), HBPin (3.4486 g, 26.946 mmol), 4,4'-di-tert-butyl-4,4'-
bipyridine (0.1446 g, 0.538 mmol), BOC—pyrrole (3.0 g, 17.960 mmol), and pentane (3
mL).The tube was taken outside the box, and heated at 60 °C for 18 h. The tube was then

taken inside the box, and the volatiles were removed under vacuum. This resulted in a

. . . . 1
brown solid. The crude reaction mixture was characterized by H NMR spectroscopy to
ensure that the reaction was complete. To this mixture was added Pd(PPh3)4 (0.5189 g,

0.449 mmol), mesityl bromide (3.5757 g, 17.960 mmol), K3PO4-nHZO (23.8688 g,

89.980 mmol), and DME (6 mL). The solution was refluxed at 100 °C for 24 h. After the
reaction was over, the solution was allowed to cool to room temperature. The volatiles

were removed under vacuum. This resulted in a brown solid. To this solid was added

K3PO4-nH20 (5.7285 g, 21.552 mmol) and BunOH (6 mL). The solution was then

refluxed at 100 0C for 24 h. The solution was allowed to cool to room temperature, and

1:1 etherszO (50 mL) was added. The solution was stirred for 15 min. The organic layer

was separated, dried over Na2SO4, and filtered. The volatiles were removed under

154

vacuum. This resulted in a dark brown solid, which was subjected to column

chromatography on silica gel with 4:1 etherzpentane solution. The product was isolated

from the first fraction as a pale brown solid in 85% (2.824 g, 15.3 mmol) yield. 1H NMR
(499.7 MHz, CDC13): 8.22 (br s, 1 H, NH), 6.92 (s, 2 H, CH—Ph), 6.85 (q, 1 H, JHH‘ 2.7
Hz, 4H—pyrrole), 6.61 (q, 1 H, JHH = 2.3 Hz, lH-pyrrole), 6.11 (m, 1 H, 4H—pyrrole),
2.30 (s, 3 H, 4-CH3-phenyl), 2.14 (s, 6 H, 2.6-CH3-phenyl). 13C {‘H} NMR (125.7

MHz, CDC13): 5 = 137.9, 136.1, 133.7, 128.1, 122.3, 117.6, 116.5, 110.3, 21.4, 21.2).

MS (EI) m/z = 185 (M+). Elemental analysis; Experimental (Calc.), C: 84.42 (84.28). H:

8.02 (8.16). N: 7.23 (7.56). M. p. 96-98 °C.

155

3-mes

Synthesis of 3-Hdap (44)

MezN

\ZI

Me

Me

A round bottom flask (250 mL) was charged with 3-mesityl pyrrole (2.2231 g, 12
mmol), formaldehyde (0.9739 g, 13.2 mmol, 37% solution), N,N-dimethylamine
hydrochloride The solution was allowed to cool to room temperature. 10% NaOH
solution (100 mL) was added, and the reaction stirred for 30 min. The reaction was then

extracted with ether (3X100 mL). The combined organic layers were washed with water

(100 mL). The final organic layer was dried over Na2SO4, filtered, and the volatiles were

removed under vacuum. This resulted in a dark brown oil, which was subjected to

column chromatography on alumina using 10% methanolzethyl acetate. The product was

isolated as brown oil in 89% yield (2.600 g, 10.7 mmol). IH NMR (499.7 MHz, CDC13):
9.78 (br s, 1 H, NH), 6.98 (s, 2 H, CH—Ph), 6.57 (s, 1 H, 2H—pyrrole), 5.98 (s, 1 H, 4H-

pyrrole), 3.62 (s, 2 H, CH2), 2.41 (s, 6 H, N(CH3)2), 2.39 (s, 3 H, 4-CH3-phenyl), 2.19
(s, 6 H, 2,6-CH3-phenyl). '3C {'11} NMR (125.7 MHz, CDC13): 8 = 137.4, 135.5, 133.6,

127.7, 126.9, 121.3, 116.8, 110.1, 56.3, 44.3, 21.2, 20.9. MS (EI) m/z = 242 (M+). M.p.

62-64 0C.

156

Synthesis of Ti(dap3'mes)2(NMe2)2 (45)

Me
Me
Me TMez
\ Nit . .ii\NM62
Tl'
N/l \NMez
Me2 N
\ /
Me
[Me
Me

All manipulations were carried out inside the glove box. A filter flask (100 mL) was

loaded with Ti(NMe2)4 in ether (1.5 mL) (0.4668 g, 2.08 mmol) and cooled inside the

cold-well. To this solution was added cold ether solution of ligand (1.0092 g, 4.2 mmol).
The solution was allowed to warm up to room temperature and stir overnight. The
solution changed to red with an orange-red precipitate. The mixture was filtered, and the

precipitate was dried under vacuum. Suitable X-ray quality crystals were grown from 1:1

dicholoromethane:pentane at -35 °C as red plates (1.0552 g, 1.71 mmol). ]H NMR (499.7
MHz, CDC13): 6.88 (s, 4 H, CH—Ph), 6.56 (d, 2 H, JHH = 1.5 Hz, 2H-pyrrole), 5.67 (d, 2
H, JHH = 1.5 Hz, 4H-pyrrole), 3.58-3.42 (br, 4 H, CH2), 3.32 (s, 12 H, N(CH3)2), 2.46

(s, 12 H, N(CH3)2), 2.28 (s, 6 H, phenyl-4-CH3), 2.18 (s, 12 H, phenyl-3,5-(CH3)2). 13C

{1H} NMR (125.7 MHz, CDC13): 137.6, 135.7, 135.3, 134.6, 127.6, 127.1, 120.6, 104.2,

63.0, 51.9, 49.1, 48.7, 21.4, 20.9. M. p. 158-160 °C.

157

Experimental for Table 3.5

Entry 2, Table 3.5:

Inside a glove box, a pressure tube was loaded with Ti(dap)2(NMe2)2 (0.0458 g, 0.119

mmol), MezNNHz (92 11L, 1.190 mmol), l-hexyne (140 uL, 1.190 mmol), tert-

butylisonitrile (136 11L, 1.190 mmol), and toluene (600 uL). The tube was taken outside

the box and heated at 100 °C for 16 h. The volatiles were removed under vacuum. This

resulted in a dark brown semisolid. To this solid was added p-OMeC6H4NHNH2-HC1

(0.2021 g, 1.190 mmol) in pyridine (2 mL). The solution was heated at 150 °C for 24 h
until the conversion was complete. The solution was then allowed to cool to room

temperature, and the volatiles were removed under vacuum. This resulted in a dark brown

semisolid which was dissolved in CH2C12 (30 mL) and extracted with water (2X25 mL).

The organic layer was collected, dried over NazSO4, and filtered. The volatiles were

removed from the filtrate under vacuum. This resulted in a brown mass, which was

characterized by 1H NMR spectroscopy. It produced the two isomers in 2:1 ratio. 1H
NMR (299.8 MHz, CDC13): 7.57 (d, 1 H, JHH = 1.7 Hz, 3H—pyrazole), 7.56-7.36 (m, 5
H, Ph), 6.19 (td, 1 H, JHH = 0.7, 1.7 Hz, 4H—pyrazole), 2.63 (t, 2 H, JHH = 7.6 Hz,

NCCHz). 1.53 (m, 2 H. NCCHZCHz), 1.29 (m, 2 H. CH2CH3), 0.85 (t, 3 H, JHH = 7.3

Hz).

158

Entry 3, Table 3.5:

Inside a glove box, a pressure tube was loaded with Ti(dap)2(NMe2)2 (0.0458 g, 0.119

mmol), MezNNHz (92 11L, 1.190 mmol), l-hexyne (140 uL, 1.190 mmol), tert-

butylisonitrile (136 11L, 1.190 mmol), and toluene (600 uL). The tube was taken outside

the box and heated at 100 °C for 16 h. The volatiles were removed under vacuum. This

resulted in a dark brown semisolid. To this solid was added p-FC6H4NHNH2 (0.1537 g,

1.22 mmol) in pyridine (2 mL). The solution was heated at 150 0C for 24 h until the
conversion was complete. The solution was then allowed to cool to room temperature,

and the volatiles were removed under vacuum. This resulted in a dark brown semisolid

which was dissolved in CH2C12 (30 mL) and extracted with water (2X25 mL). The

organic layer was collected, dried over NazSO4, and filtered. The volatiles were removed

from the filtrate under vacuum. This resulted in a brown mass, which was characterized

by 1H NMR spectroscopy as a mixture of isomers. It produced the two isomers in 4.5:]
ratio. ]H NMR (299.8 MHz. CDC13): 8.02-6.62 (m, 14 H, pyrazole, Ph), 6.24 (d, 0.46 H,
JHH = 1.7 Hz, 4H-pyrazole. minor), 6.19 (td, 1 H, JHH = 0.7, 1.7 Hz, 4H-pyrazole,
major), 3.86-3.76 (m, 7 H, OCH3), 2.79-2.56 (m, 4 H, NCCHZ), 1.83-1.55 (m, 4 H,

NCCHZCHz), 1.53-1.21 (m, 4 H, CHZCH3), 0.99-0.89 (m, 5 H, CH3).

159

Entry 4, Table 3.5:

Inside a glove box, a pressure tube was loaded with Ti(dap)2(NMe2)2 (0.0458 g, 0.119

mmol), MezNNHz (92 11L, 1.190 mmol), l-hexyne (140 1.1L, 1.190 mmol), tert-

butylisonitrile (136 11L, 1.190 mmol), and toluene (600 uL). The tube was taken outside

the box and heated at 100 °C for 16 h. The volatiles were removed under vacuum. This

resulted in a dark brown semisolid. To this solid was added p-CNC6H4—NHNH2-HC1

(0.2068 g, 1.220 mmol) in pyridine (2 mL). The solution was heated at 150 °C for 24 h
until the conversion was complete. The solution was then allowed to cool to room

temperature, and the volatiles were removed under vacuum. This resulted in a dark brown

semisolid which was dissolved in CH2C12 (30 mL) and extracted with water (2X25 mL).

The organic layer was collected, dried over NazSO4, and filtered. The volatiles were

removed from the filtrate under vacuum. This resulted in a brown mass, which was

. 1 . . .
characterized by H. NMR spectroscopy as a mixture of two different isomers. It

produced the two isomers in 1:6 ratio. 1H NMR (299.8 MHz, CDC13): 7.62 (d, 1 H, JHH

= 1.7 Hz, 3H—pyrazole), 7.78-7.36 (m, 10 H, Ph, pyrazole), 6.41-6.01 (m, 3 H, Ph), 6.31

(d, 1 H, JHH = 1.7 Hz, 4H—pyrazole. major), 6.25 (td, 0.1 H, JHH = 0.7, 1.7 Hz, 4H-
pyrazole, minor) 2.72 (m, 3 H, NCCHZ), 1.73-1.62 (m, 4 H, NCCHZCHg), 1.42-1.34 (m,

4 H, CHQCH3), 0.85 (t. 5 H, JHH = 7.3 Hz, CH3).

160

Experimental for kinetic reactions

Representative procedurefor the catalysis with 10% Ti(dap)2(NM82)2 (Case A, Table
3. 2)

Under an atmosphere of dry nitrogen, a vial was loaded with Ti(dap)2(NMe2)2 (1)

(0.0229 g, 0.060 mmol), toluene-d8 (500 11L), 1,1-Me2NNH2 (46 pL, 0.600 mol), 1-

hexyne (70 uL, 0.6 mmol), tert-butylisonitrile (68 uL, 0.600 mmol), and

hexamethyldisiloxane (0.0486 g. 0.300 mmol). The volume was adjusted to 1 mL with

toluene-d8 in a volumetric flask, and the solution was transferred to a J-Young tube. The

progress of the reaction was monitored over time at 100 °C by ]H NMR spectroscopy.

The yields were calculated with respect to internal standard (hexamethyldisiloxane). A
graph of percent yield was then plotted vs time (in min). The value of the rate constant

was calculated using OriginPro 7.5.

kobs values:

101,, = 0.84 x 10"4 s—l, R2 = 0.997
k0,, = 0.92 x 10‘4 s_l, R2 = 0.992
k0,, = 1.32 x 10‘4 s_1, R2 = 0.991
kobs= 1.18 ><10_4 s_l, R2 =0.994

Average kobs = (1.07 1 0.42) x 10’4 s—l

161

Representative procedure/er the catalysis with 10% 36 (Case B, Table 3. 2)

Under an atmosphere of dry nitrogen, a vial was loaded with 36 (0.0276 g, 0.060
mmol), toluene-d8 (500 pL), 1,1-Me2NNH2 (46 11L, 0.600 mmol), 1-hexyne (70 11L, 0.6
mmol), tert-butylisonitrile (68 11L, 0.600 mmol), and hexamethyldisiloxane (0.0486 g,
0.300 mmol). The volume was adjusted to 1 mL with toluene-d8 in a volumetric flask,
and the solution was transferred to a J-Young tube. The progress of the reaction was
monitored over time at 100 °C by 1H NMR spectroscopy. The yields were calculated

with respect to the internal standard (hexamethyldisiloxane). A graph of percent yield
was then plotted vs time (in min). The value of the rate constant was calculated using

OriginPro 7.5.

kobs values:

kobs = 0.99 x 10’4 5.], R2 = 0.999
101,, = 1.01 x 10‘4 {1,le = 0.999
10),, = 0.89 x 10’4 s—], R2 = 0.999
101,, = 1.01 x 10’4 {1,112 = 0.999

Average kobs = (0.98 i: 0.11) X 10—4 s—1

Representative procedure for the reaction of 36 with 10 equivalent Me 2NNH 2 (Case C,
Table 3. 2)

Under an atmosphere of dry nitrogen, a vial was loaded with 36 (0.0276 g, 0.060

mmol), toluene-d8 (500 uL), 1,1-Me2NNH2 (46 11L, 0.600 mmol), and

hexamethyldisiloxane (0.0098 g, 0.600 mmol). The volume was adjusted to 1 mL with

toluene-d8 in a volumetric flask, and the solution was transferred to a J-Young tube. The

progress of the reaction was monitored over time at 100 °C by 1H NMR spectroscopy.

The yields were calculated with respect to the internal standard (hexamethyldisiloxane).
A graph of percentage yield was then plotted vs time (in min). The value of the rate

constant was calculated using OriginPro 7.5.

kobs Values:

kobs = 1.08 x 10‘4 s_], R2 = 0.999
10),, = 0.94 x 10’4 s", R2 = 0.999
k0,, = 1.09 x 1074 s—], 112 = 0.998
kobs = 1.32 x 10‘4 s—l, R2 = 0.994

Average tab, = (1 .11 1 0.30) x 10‘4 s_1

163

Representative procedure for reaction with 10% 36 and 10% Hdap (Case D, Table 3. 2)

Under an atmosphere of dry nitrogen, a vial was loaded with 36 (0.0276 g, 0.060

mmol), toluene-11,6,> (500 11L), 1,1-Me2NNH2 (46 11L, 0.600 mmol), l-hexyne (70 11L, 0.6

mmol), tert-butylisonitrile (68 uL, 0.600 mmol), Hdap (0.0076 g, 0.060 mmol), and

hexamethyldisiloxane (0.0486 g, 0.300 mmol). The volume was adjusted to 1 mL with

toluene-d8 in a volumetric flask, and the solution was transferred to a J-Young tube. The

progress of the reaction was monitored over time at 100 °C by 1H NMR spectroscopy.

The yields were calculated with respect to the internal standard (hexamethyldisiloxane).
A graph of percent yield was then plotted vs time (in min). The value of the rate constant

was calculated using OriginPro 7.5.

kobs Values:

kobs = 1.19 1.10—4 s_], R2 = 0.999
kobs = 1.04 x 10‘4 5—1, R2 = 0.999
10),, = 1.19 ><1074 s—], R2 = 0.999
kobs = 1.34 x 10‘4 {1,112 = 0.999

Average kobs = (1.19 1 0.23) x 10’4 s—1

164

Represtative procedurefor the reactions shown in Table 3.3

The reactions were carried out following the procedure shown in Case A (Table 3.2)

for the kinetics experiment with 1. Only the amount of the catalyst was varied.

For Entry 1, Table 3.3. Catalyst (1) loading: (0.0349 g, 0.900 mmol)
For Entry 2, Table 3.3. Catalyst (1) loading: (0.0229 g, 0.600 mmol)
For Entry 3, Table 3.3. Catalyst (1) loading: (0.01 15 g, 0.300 mmol)

For Entry 4, Table 3.3. Catalyst (1) loading: (0.0058 g, 0.150 mmol)

X-ray Crystallography

Crystals grown from concentrated solutions at -—35 °C were moved quickly from a
scintillation vial to a microscope slide containing Paratone N. Samples were selected and
mounted on a glass fiber in wax and Paratone. The data collections were carried out at a
sample temperature of 173 K on a Bruker AXS platform three-circle goniometer with a
CCD detector. The data were processed and reduced utilizing the program SAINTPLUS
supplied by Bruker AXS. The structures were solved by direct methods (SHELXTL v5.1,

Bruker AXS) in conjunction with standard difference Fourier techniques.

165

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168

CHAPTER 4

Synthesis of Vanadium(V) hydrazido(2—)
thiolate imine alkoxide complexes

4.] Introduction

Metal hydrazido(2—) complexes are well known intermediates in dinitrogen
activation to produce NH3.]-3 Hydrazido(2—) complexes have been synthesized for a

9 i10-17

. . . 4- 18-20
large variety of metal centers including Mo and W, T r

21-24
Z , Re,

25-32 33 34 35-37 38 39 .40 41 42
V, Nb, Ta, Os, Pt, Au, Li, U, and Te. Among these,

molybdenum-based hydrazido complexes have been studied extensively due to their

. . 43 . . . . .
presence in nitrogenase enzymes. Similarly, there has been consrderable interest in

vanadium hydrazido(2—) complexes since the discovery of vanadium in the active

. . . 44-46 . . . .
Sites of Similar enzymes. The reduction of dinitrogen by these nitrogenase

enzymes is believed to involve metal-bound (Fe, Mo, V) hydrazine and hydrazido

. . 47.48 . .
intermediates. The F eMoco enzyme has been studied extensrvely and was shown

by X-ray crystallography to contain a cluster with the molybdenum atom ligated by

. 43 . .
one nitrogen, three sulfurs, and two oxygen atoms. It is generally believed that

. . . . . . . 49 . . .
vanadium in nitrogenase enzymes occupies a Similar Site. Since vanadium, like

169

molybdenum, may be the coordinating site for N2, it is important to understand the

hydrazido(2—) chemistry of vanadium with ligands containing S, N, and O atoms. In

particular, reduction of N2 to NH3 by these enzymes might involve the intermediate

' . 4 ,
spec1es N2Hm and NH" (m = 0—4, n = 0_3) bound to Vanadium. 7 48

In terms of mode of action for vanadium-containing nitrogenase, it has been

demonstrated that S3-1igated vanadium in cluster anions such as [Fe3S4X3V(DMF)3]_

(X = Cl, Br, or 1) binds hydrazines50 and imides,5] and catalyzes their reduction.

Examples and syntheses of a few vanadium hydrazido(2—) complexes will be
discussed in the following sections. For comparison, hydrazido(2—) chemistry of

adjacent titanium will be briefly reviewed.

170

4.2 Hydrazido versus isodiazene bonding in MNNRZ complexes

The degree of donation of the B—N lone pair into the M=N 11* orbital in terminal

M—N—N ligands determines participation of the two different resonance forms. Cases

where N13 is strongly donating with weak n-donation from the metal center results in

an N—N bond order ~ 2.0. This is represented as the isodiazene form (Figure 4.1,

. 52,53 . . . . . . .
right). This 1S favored in metal complexes With a low formal ox1dation state. This

is analogous to a singlet Fischer-type carbene complex, where the metal center is
present in a relatively low formal oxidation state. Conversely, in the cases where the

lower oxidation state of the metal is very reducing, e.g. titanium(II), the hydrazido(2—

. . 54-56 .
) resonance form predominates (Figure 4.1, left). Here the metal center is present

in a higher formal oxidation state, and the M—N bond order is between 2 and 3. This
situation is reminiscent of the triplet Schrock-type carbene complex where the metal
center is present in a relatively high formal oxidation state. Different reactivities have

been observed depending on the nature of the bonding in M—N—N moiety.

Figure 4.1 Hydrazido(2—) vs isodiazene resonance forms.

(9
MeeN,Me Me\w,Me
I 9
N N
Mn+ M(n-2)+
hydrazido(2—) isodiazene

171

Most often, N13 is planar in hydrazido(2—) complexes. This is observed in the

complexes where phenyl groups are present on the N13 atom in M—N—N

13,20,56

moiety. This occurs due the the conjugation of the B-nitrogen with the phenyl

ring. However, in the complexes where NB has only alkyl groups as substituents, the

. . . . . 3
geometry around the B-nitrogen atom is very different. In this case, NB lS sp -

hybridized, and the sum of the angles around it can be ~ 328.0°. Only a few examples

of hydrazido(2—) ligands with pyramidalized B-nitrogens have been structurally

. 12,14 . . . . .
characterized. In the isodiazene complexes, consrderable contribution from N13

into M=N 11* orbital results in significant delocalization of electrons in M—N—N

moiety. This results in a planar N13’ and the sum of the angles around that atom is

~36OO57,58

172

4.3 Vanadium(V) hydrazido(2—) complexes

Vanadium(V) hydrazido(2—) complexes with different ligands are known in the

literature”.31 A vanadium(V) hydrazido(2—) complex with aryloxide ligands,

MezNNV(OAr) , where Ar = 2,6-Pr12C6H has been reported (Equation 4.1).28 This
3 3

compound was very stable to reduction by zinc or Na/Hg. The hydrazido(2—) group

can not be protonated by anhydrous HCI. However, it undergoes metathesis with
N(CHZCHZSH)3 to give [V(NNMe2){N(CH2CHZS)3}], (Equation 4.2).30 This is the

first example of Vanadium(V) hydrazido(2—) complex with sulfur-donor atoms as the

ancillary ligand.

 

lltle\l N/Me
CH2C|2
(NH2Me2)21{VC|3}2(lt-NNM62)31 reflux = (4.1)
+ 6 Li(DlPP) 85% Fri
rI

G)
. 0 .
_ Pr’ Pr,
DIPP - + 6 LiCl + H2NNMe2 + 2 NHMez

Alternatively, MezNNV(OAr)3 can be prepared from the corresponding
vanadium(V) oxo compound by treating with Me3SiNHNMe2 as shown in Equation

30 . .
4.3. From the X-ray crystal structure of this compound, the V—N distance was

found to be 1.681(3) A. The N-N distance was 1.305(5) A, and the V—N-N angle was

173

l73.9(4)°. The N—N bond distance of 1.295(17) A is similar to that observed in

[vc12(NH2NMePh)2(NNMePh)]‘.3‘

Me\ /Me

 

Me\ /Me
- i
Pr’ )1; Pr
H E 1.5 N(CHZCHZSH)3
/v\
.0 l O , Hexane, 20 °C,9h
Pr’i O 0’ 87°/
Pr r °

_” Me3SiNHNMe2

S— \ (4.2)
so 8

 

Keg/NJ CHZClz, 20 °C

T’ S_ \ 4.3
Rail S ( 1

Vanadium(V) hydrazido(2—) complexes with different B-nitrogen substituents have

been reported (Equation 4.4).27 Here, the N—N bond distances in the corresponding

NNPhMe and NNHPh complexes are 1.305(5) A and 1.310(3) A, respectively.

 

174

II
S— \
. (so 3 <14)
CNJ

1 2

R =Ph,R =H,88%
R1 = Ph, R2 = Me, 65%

Hydrazido(2—) complexes were also synthesized using [O(SCH2CH2)2]2— (0S2) as
the ancillary ligand on vanadium(V).27 For example, the reaction of V(O)(OPri)3 with
2,6-di-iso-propylphenol and O(CH2CH2SH)2 generated V(OSZ)O(OAr), which was then
treated with MezNNHz to form V(OS2)(NNMe2)(OAr) as the final product (Scheme

16

4.1).

Scheme 4.1 Synthesis of a vanadium hydrazido(2—) complex with O(SCH2CH2)22—
as co-ligand

 

 

V(0)(0Pr’)3
+
. 0H .
l I
Pr Pr hexane M NNH
e V(O)(osz)(OAr) e2 2: V(NNMe2)(Osz)(OAr)
82% CH3CN
+ 55%
HS/\/0\/\SH Ar = 2,6-Pr’206H3

In a more recent example, V(NS3)(NNC5H10) was synthesized using 1-
aminopiperidine to introduce the hydrazido(2—) moiety (Equation 4.5).26 It was

synthesized by reaction of [V(NS3)O] with l-aminopiperidine at 140 °C. The V—N

distance was 1.677(2) A; the N—N distance was 1.324(3) A. The V—N—N(hydrazido)

angle is almost linear at 177.0(2)°. A derivative from benzophenone hydrazone

(Ph2C=NNH2) to give V(NS3)(NNCPh2) was also prepared (Equation 4.6).26

175

l
excess < :N‘NHZ hl

 

 

140 °C, neat is/ l S

78% CNV

Ph\ ,Ph
1?
Ph\ N
C=N-NH2 N

Ph’ 3 ll (4 6)
—> _ \ .

diglyme, 160 °C, 30 min XS—h S

45% K/

176

4.4 Titanium hydrazido(2—) complexes

A handful of examples of terminal Group-4 hydrazido(2—) complexes are known in

the literature. The first example of a terminal titanium hydrazido(2—) complex, e.g.

Cp2Ti{NN(SiMe3)2}, was reported in 1978 by Wiberg and co-workers.17 In 1999,

Mountford’s group reported tetraazamacrocycle-supported titanium and zirconium

hydrazido(2—) complexes and their reactions with carbon dioxide, isocyanide, and

isocyanates.l6 Woo and Thorrnan developed porphyrin-based hydrazido(2—) complexes
of titanium.‘5 The first crystallographically characterized terminal titanium hydrazido(2—
) complex, Ti(NNMe2)(dpma)(But-bpy), where dpma = N,N-di(pyrrolyl-a-methyl)-N-
methylamine, and But-bpy = 4,4'-di-tert-butyl-2,2’-bipyridine, was reported by our group

in 2004 (Equation 4.7).14

\ NMez
01 NM
/ NI/l 32
t NMez
/ \ |
Me \ N l
@‘l’li‘imN ~_/ But
* T / Nfl‘""‘ 3“ “'7’
N N— o / I“ \
/ \ \ / 72/o Me
But But
+
Me2NNH2

I77

Another example of a structurally characterized titanium hydrazido(2—) complex from

our group was Ti(NNMe2)(dap)(nacnac), where dap = 2-(dimethylaminomethyl)pyrrolyl
and nacnac = [N(But)CHCHC(Bun)N(NMe2)-k2N] (Equation 4.8). Complex (36) was

prepared as a possrble intermediate in iminohydrazmation of alkynes (the supra).

 

 

TMez
n _ NMez
BU :— H _ N [L Bun
ll -«,
Ti(dap)2(NMe2)2+ H2NNMe2 = \ ”\Ti/ 2 (4.8)
1 . toluene, RT N/ \N'J
_ t 94% M92 ’
CN Bu But
36

More recently, a series of terminal titanium(IV) hydrazido(2—) complexes were

reported.” The complexes were synthesized by the addition of bpy, where, bpy = 2,2'-

bipyridine, to a solution of Ti(dpma)(NMe2)2 followed by substituted hydrazines

(Equation 4.9). In contrast to the normal yellow to red color of titanium(IV) complexes,
these complexes are blue to green. This is due to an unusual low-energy ligand to ligand
charge transfer (LLCT) transition from the hydrazido(2—) ligand to an empty 11* orbital of

bipyridine.

In 2005, Mountford described the synthesis and bonding analysis of both terminal

and bridging hydrazido(2—) complexes of titanium. The terminal complex was

178

synthesized by reacting Ti(NMez)2C12 with thNNHz (Scheme 4.2).13 In contrast,

sterically smaller substituents on the hydrazines, such as MezNNHZ or N-

aminopiperidine, yielded bridging hydrazido(2—) complexes as shown in Scheme 4.2.

 

\ NMez
01- NM
/ 1"- e
/ ”I l 2
/ II.,N\
Me 2 3
+ R\N/R
|
N N_ ‘ N 1
/ \ = @‘Jl-liumN ‘—/ R1 (49)
_ \ / ether / er‘N ’—\ R
R1 R1 33—72% / N
Me
4.
R2\ R1 =H, Me, Ph, But
NNH2 2
| =H, Me
3 3
R R =Me,Ph,p-tol,p-FC6H4

I79

Scheme 4.2 Synthesis of titanium hydrazido(2—) complexes

Ph2NNH2

MezNNHz
Ti(NMeg)2C|2

 

ll

Ph. ,Ph
'1
N
l}.
MezHN’s '\\NHMe
Cl CI 2
Meg
N
/
MeZHNI Tii-‘\/N\\T “Cl
MezHN’T \ N//I\ CI
N
Me2
2%

MeZHNI (Ti/N/\\Tit‘ (\CI
MeZHN’ \ N//T \Cl

33

Ti(NNPh2)C12(NHMe2)2, synthesized according to Scheme 4.2, has been used to

synthesize a variety of hydrazido(2—) complexes by metathesis with a fac-N3 donor

ligands as shown in Scheme 4.3.13

180

Scheme 4.3 Synthesis of titanium hydrazido(2—) complexes with different fac-N3
donor ligands

Me
Me VN
N /N/\-_ jN— Me
C—Q Me /T'
— 2'”
N - N N/ ”\C lCl
Me] ‘2 / Me Ph\
T , N
/N// \‘Cl \
Pth Cl / Ph
\
Ph M6319]aneN3 PhsN’Ph Me3[6]aneN3
l
N
u.
Me2HN’s '\\NHMe2
Cl CI
HC(4-Bu"pz)3 HC(Me292)3

H

(2 Me flg\{\fleMe
441 11141181] Cl .11

Me ‘ /Me Me
;Ti-../ "Cl //Ti""'Cl
N \

\

Ph\N‘/N/ Cl N
1

Ph Ph
In additon, both sandwich and half-sandwich complexes of titanium carrying
hydrazido(2—) ligands have been reported. They were synthesized from the
corresponding imido complexes by reacting with hydrazine as shown in Scheme

4.4.]0

181

Scheme 4.4 Synthesis of titanium hydrazido(2—) complexes from imido complexes

 

RQR R'2NNH2 . R R
R I. R > I R l. R
waTl§ Pr\ /TI\
Ll ”\But )NSN/ \ ‘NR2
Me ‘ i
R=HorMe;n=1or0 Pr
. R=Me
L = CI, MeC(NPr’)2 or C5H5 R' = Ph, Me

Ph2NNH2

 

182

Ph2NNH2

R: g. R

'. R
PWT'SN
Cl \Nth

4.5 Aim of the current project

Although different types of vanadium(V) hydrazido(2—) complexes are known in
the literature, no examples of vanadium hydrazido(2—) complexes are known where
all of the elemental connections found in the enzyme, e.g., S, N, and O, are in the

same coordination sphere. As part of our ongoing interest in the study of transition

ll,lZ,l4 .
we pursued the syntheses of vanadium(V)

metal hydrazido(2—) complexes,
hydrazido(2—) complexes with a chelating ligand containing a thiolate, alkoxide, and
donor imine, 2-((2-thiol-pheny1imino)methylene)phenol HZTIP, Equation 4.10.25 The

synthesis of different vanadium(V) hydrazido complexes with this ancillary ligand

will be discussed in the following sections.59

 

OH 0 SH
©:NH ethanol, reflux, 4 h ( )
2 31% H
H2TIP

l83

4.6 Results and Discussion

In order to synthesize vanadium(V) hydrazido(2—) complexes with the TIP

ancillary, we initially attempted direct reaction of HZTIP with V(NNMez)(OAr)3,28
where Ar = 2,6-Pri2C6H3. Unfortunately, these reagents did not result in the
elimination of 2 ArOH and the synthesis of V(NNMe2)(OAr)(TIP) (47). However, we
were able to readily synthesize (Me3Si)2TIP (46) which on reaction with

V(NNMe7_)(OAr)3 produced 47 in good yield (Scheme 4.5).

Scheme 4.5 Synthesis of V(NNMe2)(OAr)(TlP) (46) (where Ar = 2,6-Pr’2C6H3)

SiMe3

@SH excess ISiMe3 as
4 NEt ‘
N OH 3 ~ N o’S'Me3

V

toluene, cold—RT, 12 h
H 87% H

H2T|P ’ (SiMe3)2TIP (46)

Me2NNV(OAr)3
toluene, 120 °C, 2 d
74%

 

lTlMez

N
|,\S

i /\'Q
Pr 0 NW\
.\
r:

47

I84

In order to explore the chemistry of the V(NNMe2)(TIP) framework further, we

exchanged the aryloxide ligand in 47 with iodide. Treatment of 47 with ISiMe3 in

toluene eliminated Me3SiOAr and produced V(NNMe2)(TIP)(I) (48) in 95% crude

yield (Equation 4.11). The iodide complex was quite insoluble in most solvents but

was effective as a starting material without further purification.

 

1'1 'SiMGB "v NNM I TIP " 411
V(NNMe2)<SN0><TIP) toluene , ( erX > ( . >
47 95% crude yield 48

A brown suspension of 48 in CHzClz reacted with dmpe, l,2-
(dimethylphosphino)ethane, to generate a dark red solution (Scheme 4.6). The new
complex, [V(NNMe2)(TIP)(dmpe)]I (49), was isolated in 62% yield. Similarly,
treatment of 48 with 4,4'-tert-butyl-2,2'-bipyridine (Butbpy) and triflate or

hexafluoroantimonate silver(l) salts formed cationic, hexacoordinate complexes in

good yields (Scheme 4.6).

I85

Scheme 4.6 Synthesis of cationic hydrazido(2—) complexes

 

   
  

 

 

e
- NMe2 7
f—\ M62111
Me2P PMe2 p“ II ,S 9
"V(NNMe2)(I)(TIP)" T Cp’)" \0 1
01-12012 N(\\
48 Nl
62% M92 V
Butbpy,AgX 49
CHZCIZ
_ e
NMez "

But Nu, $fo 6)
But N/l N(\\0 [x]
g v©

 

 

50 = x” = ‘SbF6, 30%
51 = x‘ = ‘OTf, 31%

The dmpe complex 49 was characterized by single crystal X-ray diffraction, and

an ORTEP representation is shown in Figure 4.2. Unlike the titanium

dimethylhydrazido(2— ) complexes reported, H 12 M this hexacoordinate complex has

a planar Me—N—Me moiety, which is common for hydrazido(2—) complexes of most

metals.56 This cationic complex has a short N—N bond of 1.293(3) A. The shortest

hydrazido N—N distance was found in an iron porphyrin complex, and was measured

as ~1.232(5) A.53 The metric parameters in the hydrazido ligand are similar to a
related cationic vanadium complex reported by Dilworth and co-workers.“ The short

N—N bond is indicative of a double bond, and the NNMez ligand in this case may be

I86

better described as an isodiazene (Figure 4.3, (a)). However, the metric parameters of

V—N—N moiety in 49 are different from the known vanadium bis(isodiazene)
complex, [(Cng8N2)2(OSiMe3)2(OSiMe3)2V(u-O)V(O)(OSiMe3)2] (52) (Figure

4.3, (b)). The selected bond lengths and bond angles in 52 are as follows: V—N =

1.725(2) — 1.781(3) A, N—N = 1.285(3) — 1.245(4) A, V—N—N = 176.4(2)°,
174.3(2)°.34 Thus compound 49 can not be unambiguously described as an isodiazene

complex. While quite different from hydrazido(2—) ligands of titanium in many
respects, the short V=N bond in 49 of 1.698(2) A suggests a significant contribution

from the hydrazido(2—) resonance form as well.

Figure 4.2 ORTEP representation of the cationic part in 49. Hydrogens and iodide ion
are not shown. Ellipsoids are drawn at the 50% probability level. Selected bond
lengths (A) and angles (°): V(1)—N(1) 1.698(2), N(1)—N(2) 1.293(3), V(1)—O(1)
1.908(2), V(1)—N(3) 2.162(2), V(1)-S(1) 2.3383(8), V(1)—P(1) 2.5078(8), V(1)—P(2)
2.5079(8), N(2)—N(1)—V(1) 168.5(2), O(l)—V(l)—S(l) 119.53(6).

‘,I

l.__\
\ I“:

 

187

Figure 4.3 (a) Hydrazido(2—) vs isodiazene resonance forms in vanadium complex. (b)

Structure of 52.
M \ ’M \®/
(a) e N e Me h. Me (6)
9N
1' <—> ‘
V5+ V3+
hydrazido(2—) isodiazene

188

M e

e
Me

// \ I e3

/N 0

N e \\//<0

Me | OSiMe3
'M

52 OSI 63

4.7 Concluding Remarks

Using readily prepared V(NNMe2)(OAr)3 as a starting material, an example of a

hydrazido(2—) TIP complex, V(NNMe2)(OAr)(TIP) (46) where Ar = 2,6-Pr’2C6H3,
can be prepared. Replacement of the OAr ligand with iodide proceeds smoothly with
lSiMe3. While iodide 48 was not fully characterizable due to very low solubility in

common solvents, it served as starting material for cationic hydrazido complexes. An

X-ray diffraction study on one of the cationic vanadium complexes,

[V(NNMe2)(TIP)(dmpe)]I (49), revealed a quite short N—N bond. This short N—N

bond is indicative of the V(llI) cation having poor backbonding into the N=N 7t*

orbital of the isodiazene.

189

4.8 Experimental
General Considerations

All manipulations of air sensitive compounds were carried out in an MBraun
drybox under a purified nitrogen atmosphere. Pentane (Spectrum Chemical Mfg.
Corp.), toluene (Spectrum Chemical Mfg. Corp.), ether (Columbus Chemical
Industries Inc.), dichloromethane (EM Science), acetonitrile (Spectrum Chemical),

and tetrahydrofuran (JADE Scientific) were sparged with nitrogen to remove oxygen

then dried by passing through activated alumina. VC13(THF)3 was purchased from

Strem Chemical Co. and used as received. 1,1-dimethylhydrazine was purchased from

Aldrich Chemical Co. and distilled from KOH prior to use. 4,4'-di-tert-buty1-2,2’-

bipyridine (Butbpy) was purchased from Aldrich Chemical Co. and used as received.

H2TIP25 and V(NNMe2)(OAr)328 were synthesized according to the literature

procedures. Deuterated solvents were dried over purple sodium benzophenone ketyl

(C6D6) or phosphoric anhydride (CDC13) and distilled under nitrogen. 1H and 13C
NMR spectra were recorded on lnova 300 or VXR-SOO spectrometers. 1H and 13C
NMR spectral assignments were confirmed, when necessary, with the use of 2-D 1H—

1 13 1 . . . . . 13
H and C— H correlation NMR experlments. Routlne couplmg constants 1n C

NMR spectra are not reported. All spectra were referenced internally to residual

protiosolvent (111) or solvent (13C) resonances. Chemical shifts are quoted in ppm

and coupling constants in Hz.

190

Synthesis of (Me3Si)2TIP (46)

SiMe3
S

CEN O,SIMe3
HJK©

All the manipulations were carried out inside an inert atmosphere glove box. An
Erlenmeyer flask (100 mL) was loaded with H2TIP (1.00 g, 4.36 mmol) and toluene
(1.5 mL). The solution was cooled in a liquid nitrogen cooled cold well inside the
box. Triethylamine (1.78 g, 17.6 mmol) in toluene (0.5 mL) was added to the
solution. Trimethylsilyl iodide (3.52 g, 17.6 mmol) in toluene (0.5 mL) then was
added. After the additions, the reaction was then allowed to warm to room
temperature and stir overnight. The reaction mixture became pale yellow with a white
precipitate. The precipitate was filtered with a fritted funnel, and the volatiles were

removed in vacuo. The product was collected as a viscous, pale yellow oil in 87%

yield (1.43 g, 3.9 mmol). 1H NMR (299.8 MHz, C6D6): 7.56 (d, J = 7.48 Hz, 1 H,
imine-CH), 7.01-6.61 (m, 8 H, aryl), 0.23 (s, 9 H, SiCH3), 0.15 (s, 9 H, SiCH3).

‘3C{‘H} NMR (125.7 MHz, C6D6): 150.7, 147.9, 136.1, 128.3, 128.0, 126.2, 124.8,

122.5, 121.4, 120.0, 118.0, 110.7, 64.9, 0.69, 0.23.

191

Synthesis of V(NNMe2)(TlP)(OAr) (47)
NMez

N
HAS

i /\'o
Pr 0 {,0
,V
rI

Under an atmosphere of dry nitrogen, a threaded pressure tube was loaded with

V(NNMe2)(OAr)3 (1.50 g, 2.30 mmol) and (SiMe3)2TIP (0.87 g, 2.30 mmol) in

toluene (9 mL). The pressure tube was taken outside the box and heated at 120 °C for
2 d. After cooling the tube to room temperature, the reaction mixture was filtered
using a fritted funnel. Volatiles were removed from the brown filtrate in vacuo. This
resulted in a dark brown solid. The brown solid was washed with cold pentane, and

the residue was dried in vacuo. Finally, the product was crystallized as a dark brown

solid from 1:1 etherzpentane in 74% yield (0.87 g, 1.70 mmol). 1H NMR (499.7 MHz,
C6D6): 9.21 (S, 1 H, imine-CH), 7.82 — 6.76 (m, 11 H, aryl-CH), 3.08 (s, 6 H, NCH3),
2.80 (m, 2 H, CHMez), 0.84 (d, 6 H, JHH = 6.9 Hz. CHCH3), 0.81 (d, 6 H, JHH = 6.8

Hz. CHCH3). '3C{'H} NMR (75.4 MHz, CDC13): 167.2, 159.5, 147.8, 145.4, 134.8,

134.3, 134.0, 128.0, 127.2, 124.3, 122.3, 121.6, 120.7, 119.5, 119.4, 116.7, 43.8, 26.2,

22.9, 22.5. 51v NMR (131.6 MHz, CDC13): 215.2 (DI/2 = 1813 Hz). Elemental

analysis: Exp. (Calc.), C: 63.47 (63.17); H: 6.44 (6.24); N: 8.00 (8.19). M.p.: 152-154

°C.

192

Synthesis of V(NNMe2)(TlP)(I) (48)

Under an atmosphere of dry nitrogen, a threaded pressure tube (20 mL) was

loaded with V(NNMe2)(TIP)(OAr) (0.76 g, 1.50 mmol) and ISiMe3 (0.33 g, 1.70

mmol) in toluene (6 mL). The solution was then heated at 45 °C overnight. A brown
precipitate appeared from the reaction mixture. The precipitate was filtered using a
fritted funnel. The solid was dried in vacuo. The product was isolated as brown
powder in 95% crude yield (0.66 g, 1.40 mmol). Several attempts to purify this
compound were unsuccessful as it was highly insoluble, and the compound was used

without further purification. M.p. 216-218 °C.

193

Synthesis of [V(NNMe2)(TIP)(dmpe)]l (49)

—-

/
“o

 

 

Under an atmosphere of dry nitrogen, a vial (20 mL) was loaded with

V(NNMe2)(TIP)(l) (0.18 g, 0.39 mmol), and the powder was suspended in CHZCIZ

(1.9 mL). To the stirred suspension was added dmpe (0.058 g, 0.39 mmol). The
mixture was stirred overnight. The brown suspension gradually turned into a bright

red solution. The volatiles were removed in vacuo. The product was crystallized from

1:1 CHzClzzTHF in 62% yield (0.15 g, 0.24 mmol). 1H NMR (499.7 MHz, CDC13):
9.47 (S, 1 H, imine-CH), 8.19 (s, 1 H, aryl-CH), 7.93 (d, 1 H, JHH= 7.6 Hz, aryl-CH),
7.70 (t, 1 H, JHH = 4.5 Hz, aryl-CH), 7.65 (t, 1 H, JHH = 7.6 Hz, aryl-CH), 7.34 (q, 2
H, JHH = 2.4 and 3.0 Hz, aryl-CH), 7.28 (d, 1 H, JHH = 8.34 Hz, aryl-CH), 7.18 (t, 1
H, JHH = 6.8 Hz, aryl-CH), 3.69 (s, 6 H, NCH3), 2.11-2.03 (br s, 2 H, CH2), 1.78-
1.75 (dd, 6 H, J = 1.7 and 10.3 Hz, PCH3), 1.78-1.66 (br s, 2 H, CH2), 0.54-0.37 (dd,

6 H, J= 9.9 and 10.3 Hz. PCH3). 13C{1H} NMR (125.7 MHz, CDCI3): 165.6, 164.7,

149.8, 144.1, 144.1, 134.9, 134.7, 129.2, 127.3, 126.1, 121.7, 121.2, 119.2, 44.2, 29.3

(dd, JCP = 12.5 and 27.5 Hz, CH2), 25.2 (dd, JCp = 9.6 and 26.8, CH2). 18.9 (dd, JCp

= 3.0 and 27.8, PCH3), 14.6 (dd, JCP = 17.2 and 22.2, PCH3). 3‘P('H} NMR (200

194

MHz): 39.2 (br s). 5'v NMR (131.6 MHz, CDC13): —21.7 (01/2 = 1382 Hz).

Elemental analysis: Exp. (Calc.), C: 41.11 (41.12); H: 5.15 (5.09); N: 6.77 (6.85).

M.p.: 179-181°C.

195

Synthesis of [V(NNMe2)(TIP)(Butbpy)][SbF6] (50)

_ _ (+3
NMez

N
But \_,Nn,,'_\“/‘,\§ 9
But:\_§N/fil(|\\\o [NMe2l

e®

— -_

 

 

Under an atmosphere of dry nitrogen, a filter flask (125 mL) was loaded with 2

(0.30 g, 0.65 mmol) and CH2C12 (30 mL). The filter flask was cooled inside a liquid
nitrogen cooled cold well. Two separate vials (20 mL) were loaded with Bu’bpy (0.17
g, 0.65 mmol) and AngF6 (0.21 g, 0.61 mmol). To each reagent vial was added
CHzClz (0.5 mL). Both the vials were cooled inside the cold well. The cold solution
of Butbpy was added to the filter flask. The mixture was allowed to stir for 10 min

followed by addition of the AngF6 suspension. The reaction mixture then was

allowed to warm up to room temperature, sealed, and stirred overnight. The dark
brown suspension gradually turned into a reddish-purple solution. The volatiles were
removed in vacuo. Then solid products were stirred with THF (25 mL), and Ag]
separated as a grey solid. The solid was filtered using a fritted funnel. The volatiles

were removed in vacuo from the filtrate resulting in a reddish-purple solid containing

the crude product. The product was crystallized from 1:1 CHzClzzpentane in 80%
yield (0.34 g, 0.48 mmol). IH NMR (299.8 MHz, CDC13): 8.82 (d, 1 H, JHH = 6 Hz,

bpy-CH), 8.77 (d, 1 H, JHH = 6 Hz, bpy-CH), 8.73 (s, 1 H, imine CH), 7.84-6.83 (m,

196

12 H, aryl-CH and bpy-CH), 3.76 (s, 6 H, NCH3), 1.22 (s, 9 H, CCH3), 1.20 (s, 9 H,

CCH3). '3C{'H} NMR (75.4 MHz, CDC13): 166.2, 165.9, 164.7, 163.0, 155.8, 153.2,

152.3, 150.4, 149.1, 147.6, 134.7, 134.1, 127.08, 127.06, 125.7, 122.7, 122.3, 121.7,

121.5, 119.5, 119.1, 118.2, 117.7, 43.6. 35.5, 29.99, 29.92. 51V NMR (131.6 MHz,

CDC13): 423.8 (01/2 = 2832 Hz). Elemental analysis: Exp. (Calc.), C: 47.74 (47.16);

H: 4.82 (4.68); N: 8.01 (8.33). M.p.: 186-188 °C.

197

Synthesis of [V(NNMe2)(TlP)(Butbpy)][OSOZCF3] (51)

_ _ Er)
NMez

But \_’ N11,,“\IN}.\\§ e

But:\—.;N/ 1E0 [OTf]
N I

\s

— —l

 

 

Under an atmosphere of dry nitrogen, a filter flask (125 mL) was loaded with 3

(0.30 g, 0.65 mmol) and CH2C12 (30 mL). The filter flask was cooled inside a liquid
nitrogen cooled cold well. To the suspension was added a cold solution of Butbpy
(0.17 g, 0.66 mmol) in CH2C12 (10 mL) followed by a cold suspension of AgOTf

(0.17 g, 0.65 mmol) in CH2C12 (5 mL). The reaction mixture was allowed to warm up

to room temperature and stir overnight. The brown suspension gradually turned into a
dark purple solution. The volatiles were removed in vacuo resulting in a dark purple
solid. The solid was stirred in THF (25 mL) for 5 h. Agl separated as a grey solid,
which was filtered away using a fritted funnel. The volatiles were removed in vacuo

from the filtrate. The product was crystallized from 1:1 THszentane in 81% yield

(0.31 g, 0.49 mmol). 1H NMR (299.8 MHz, CDCl3): 8.87 (d, 1 H, JHH = 8 Hz, bpy-
CH), 8.80 (d, l H, JHH = 8 Hz, bpy-CH), 8.79 (s, 1 H, imine-CH), 7.96—6.84 (m, 12
H, bpy-CH and Ph-CH), 3.75 (s, 6 H, H3CN), 1.27 (S, 9 H, CCH3), 1.23 (s, 9 H,

CCH3). 13C{'H} NMR (75.4 MHz, CDC13): 166.3, 166.0, 164.8, 163.2, 155.9, 153.1,

152.3, 150.6, 149.1, 1.47.6, 134.6, 134.3, 127.2, 125.6, 122.7, 122.3, 121.5, 119.9,

198

119.4. 118.4, 117.7, 43.6, 35.6, 30.1, 30.0. ”1? NMR (282.4 MHz, CDC13): 5 = —79.4.

51v NMR (131.6 MHz, CDC13): 423.6 (1)1/2 = 2046 Hz). Elemental analysis: Exp.
(Calc.), C: 54.43 (54.18); H: 5.07 (5.22); N: 9.18 (9.29). M.p.: 178-180 °C.

Crystal Structure Determination of [V(NNMe2)(TIP)(dmpe)]I (49): A red needle

crystal with dimensions 0.28 X 0.12 X 0.10 mm was mounted on a Nylon loop using
paratone oil. Data were collected using a Bruker CCD diffractometer equipped with
an Oxford Cryostream low-temperature apparatus operating at 173 K. Data were

measured using (0 and (11 scans of 0.5°/frame for 10 s. The total number of images

was based on results from the program COSMO6O where redundancy was expected to

be 4.0 and completeness of 100% out to 0.83 A. Cell parameters were retrieved using
APEX 11 software and refined using SAINT on all observed reflections. Data
reduction was performed using the SAINT software. Scaling and absorption
corrections were applied using SADABS multi-scan technique supplied by George

Sheldrick. The structure was solved by the direct method using the SHELXS-97

program and refined by the least squares method on F2, SHELXL-97, incorporated in

SHELXTL-PC V 6.10. The structure was solved in the space group Pbca. All non-
hydrogen atoms are refined anisotropically. Hydrogens were calculated by

geometrical methods and refined as a riding model. Crystal Data:

C21H3IIN3OPZSV, M: 613.33, orthorhombic, a = 10.8685(2) A, b = 18.3385(3) A, c
= 26.2108(5) A, U = 5224.13(16) A3, space group Pbca, Z = 8, 67170 reflections were

collected, 6199 were unique (Rim = 0.0556) which were all used in calculations. The

199

final R1 = 0.0566 and wR(F2) = 0.0701 for all data. The final R] = 0.0325 and wR(F2)

= 0.0627 for all data 1 > 26(1).

200

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(a) COSMO V1.56, Software for the CCD Detector Systems for Determining Data
Collection Parameters. Bruker Analytical X-ray Systems, Madison, WI (2006); (b)
APEX2 V 1.2-0 Software for the CCD Detector System; Bruker Analytical X-ray
Systems, Madison, WI (2006); (c) SAINT V 7.34 Software for the Integration of
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204

TlTANIUM-CATALYZED ADDITIONS OF SUBSTITUTED HYDRAZINES TO
ALKYNES: CATALYST DESIGN, MECHANISTIC STUDIES, AND
APPLICATIONS IN HETEROCYCLE SYNTHESIS

VOLUME 11

By

Sanj ukta Banerjee

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Chemistry

2008

APPENDIX A

Crystallographic information

Table Al.1 Crystal data of Hzenp (4)

Identification code
Empirical formula

Formula weight
Temperature
Wavelength
Crystal system
Space group

Unit cell dimensions

Volume

Z

Density (calculated)
Absorption coefficient

F(000)

Crystal size

Theta range for data collection

Index ranges

Reflections collected

eyb011_0m

C14 H22 N4

246.36

173(2) K

0.71073 A

Triclinic

P -1

a = 8.5225(2) A alpha: 109.2960(10)°.
b = 9.2895(2) A beta= 104.2810(10)°.
c = 9.5622(2) A gamma = 93.0310(10)°.
684.91(3) A3
2

1.195 Mg/m3

0.074 mm—1
268

0.23 x 0.20 x 0.18 mm3

2.35 to 27.49°.
—10<=h<=11,—12<=k<=12,—12<=l<=12
9850

205

Independent reflections 3074 [R(int) = 0.023 7]
Completeness to theta = 25.00° 99.8 %
Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.9868 and 0.9833

Full-matrix least-squares on F 2

3074/0/165

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2 1.060
R1 = 0.0446, wR2 = 0.1155
R1 = 0.0545, wR2 = 0.1223

Final R indices [I>23igma(l)]
R indices (all data)

Largest diff. peak and hole 0.274 and -0.209 e.A’3

Table A1.2 Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Hzenp. U(eq) is defined as one third
of the trace of the orthogonalized Uil tensor

 

 

x y 2 U(eq)
N(I) 28(1) 2531(1) 5468(1) 27(1)
N(2) 3391(1) 3502(1) 5086(1) 21(1)
C(l) —1417(2) 1539(2) 4869(2) 32(1)
C(2) -2009(2) 1334(2) 3349(2) 31(1)
C(3) -874(2) 2229(2) 2997(2) 28(1)
C(4) 375(2) 2964(2) 4327(2) 23(1)
C(5) 1847(2) 4074(2) 4607(2) 26(1)
C(6) 3536(2) 2092(2) 3887(2) 31(1)
C(7) 4826(2) 4699(2) 5615(1) 24(1)
N(3) 4296(1) 2663(1) 7863(1) 23(1)
N(4) 1139(1) 3479(1) 8872(1) 22(1)
C(8) 5483(2) 1730(2) 7740(2) 26(1)
C(9) 5963(2) 1424(2) 9074(2) 27(1)

206

C(10)
C(11)
C(12)
C(13)
C(14)

5026(2)
4006(2)
2850(2)

508(2)

93(2)

2203(2)
2965(1)
4032(2)
2067(2)
4694(2)

10043(2)

9273(1)
9800(2)
9039(2)
9178(1)

25(1)
22(1)
24(1)
33(1)
25(1)

 

Table Al.3 Bond lengths (A) and angles (°) for Hzenp

 

N(1)-C(4)
N(1)—C(l)
N(1)-H(1)
N(2)-C(6)
N(2)-C(5)
N(2)-C(7)
C(1)-C(2)
C(1)-H(1A)
C(2)-C(3)
C(2)-H(2)
C(3)-C(4)
C(3)-11(3)
C(4)-C(5)
C(5)-H(5A)
C(5)-H(5B)
C(6)-H(6A)
C(6)-H(6B)
C(6)-H(6C)
C(7)-C(7)#1
C(7)-H(7A)

1.3692(17)
1.3703(18)
0.8800
1.4624(17)
1.4704(16)
1.4721(16)
1.360(2)
0.9500
1.414(2)
0.9500
1.3771(18)
0.9500
1.4916(18)
0.9900
0.9900
0.9800
0.9800
0.9800
1.541(2)
0.9900

207

C(7)-H(7B)
N(3)-C(8)
N(3)-C(1 1)
N(3)-H(3A)
N(4)-C(13)
N(4)-C(12)
N(4)-C(14)
C(8)-C(9)
C(3)-11(8)
C(9)-C(10)
C(9)-H(9)
C(10)-C(1 1)
C(10)-H00)
C(1 1)-C(12)
C(12)-H(12A)
C(12)-H(12B)
C(13)-H(13A)
C(13)-H(13B)
C(13)-H(13C)
C(14)-C(14)#2
C(14)-H(14A)
C(14)-H(14B)

C(4)-N(1)-C(1)
C(4)-N(1)-H(1)
C(1)-N(1)-H(1)
C(6)-N(2)-C(5)
C(6)-N(2)-C(7)
C(5)-N(2)-C(7)
C(2)-C(1)-N(1)
C(2)-C(1)-H(1A)

0.9900
1.3679(16)
1.3706(16)
0.8800

1 .4632(17)
1.4691(16)
1.4740(15)
1.3671(19)
0.9500
1.4158(19)
0.9500
1.3757(17)
0.9500
1.4920(17)
0.9900
0.9900
0.9800
0.9800
0.9800
1.536(2)
0.9900
0.9900

109.16(11)
125.4
125.4
111.37(11)
112.87(10)
112.3700)
108.78(13)
125.6

208

N(l)-C(1)-H(1A)
C(1)-C(2)-C(3)
C(ll-C(2)-H(2)
C(3)-C(2l-H(2)
C(4)-C(3)-C(2)
C(4)-C(3)-H(3)
C(2)-C(3)-H(3)
N(ll-C(4)-C(3)
N(ll-C(4)-C(5)
C(3)-C(4)-C(5)
N(2)-C(5)-C(4)
N(2)-C(5)-H(5A)
C(4)-C(5)-H(5A)
N(2)-C(5)-H(5B)
C(4)-C(5)-H(5B)
H(5A)-C(5)-H(5B)
N(2)-C(6)-H(6A)
N(2)-C(6)-H(6B)
H(6A)-C(6)-H(6B)
N(2)-C(6)-H(6C)
H(6A)-C(6)-H(6C)
H(6B)—C(6)-H(6C)
N(2)-C(7)-C(7)#1
N(2)-C(7)-H(7A)
C(7)#1-C(7)—H(7A)
N(2)-C(7)-H(7B)
C(7)#l-C(7)-H(7B)
H(7A)-C(7)—H(7B)
C(8)-N(3)-C(1 1)
C(8)-N(3)-H(3A)
C(1 1)-N(3)-H(3A)

125.6
106.8503)
126.6
126.6
107.9302)
126.0
126.0
107.2802)
122.740 1)
129.9602)
1 12.8200)
109.0
109.0
109.0
109.0
107.8
109.5
109.5
109.5
109.5
109.5
109.5
115.970 3)
108.3
108.3
108.3
108.3
107.4
109.470 1)
125.3
125.3

209

C(13)-N(4)-C(12) 1 1 1.3700)

C(13)-N(4)-C(14) 1 12.9600)
C(12)-N(4)-C(14) 1 12.0600)
C(9)-C(8)-N(3) 108.4602)
C(9)-C(8)-H(8) 125.8
N(3)-C(8)-H(8) 125.8
C(8)-C(9)—C(10) 106.8602)
C(8)-C(9)—H(9) 126.6
C(10)-C(9)-H(9) 126.6
C(1 1)-C(10)-C(9) 107.9402)
C(1 1 )-C(10)-H(10) 126.0
C(9)-C(10)-H(10) 126.0
N(3)-C(11)-C(10) 107.2701)
N(3)-C(11)-C(12) 122.5201)
C(10)-C(1 1)-C(12) 130.0802)
N(4)-C(12)-C(1 1) 113.3800)

N(4)-C(12)-H(12A) 108.9
C(11)-C(12)-H(12A) 108.9
N(4)-C(12)-H(IZB) 108.9
C(11)-C(12)-H0213) 108.9
H(12A)-C(12)-H023) 107.7
N(4)-C(13)-H(13A) 109.5
N(4)-C(13)-H(13B) 109.5
H(I3A)-C(13)-H(13B) 109.5
N(4)-C(13)-H(13C) 109.5
H(l3A)—C(13)—H(13C) 109.5
H(13B)-C(l3)—H(13C) 109.5
N(4)-C(14)-C(14)#2 1 16.1203)
N(4)-C(14)-H(14A) 108.3
C(14)#2-C(14)-H(14A) 108.3
N(4)-C(14)-H(14B) 108.3

210

C(14)#2-C(l4)-H(14B) 108.3
H(14A)-C(14)-H(14B) 107.4

 

Symmetry transformations used to generate equivalent atoms:
#1 -x+1,-y+l,-z+1 #2 -x,-y+1,-z+2

Table Al.4 Anisotropic displacement parameters (A2 X 103)for Hzenp. The anisotropic
displacement factor exponent takes the form: -2 pi2 [ h2a*2 U11 + + 2 h k a* b* U12 ]

 

 

ull u22 u33 u23 ul3 ul2
N(l) 21(1) 34(1) 24(1) 9(1) 6(1) 0(1)
N(2) 18(1) 22(1) 24(1) 8(1) 7(1) 1(1)
C(1) 24(1) 37(1) 37(1) 14(1) 13(1) -2(1)
C(2) 23(1) 31(1) 33(1) 4(1) 7(1) -2(1)
C(3) 25(1) 32(1) 25(1) 8(1) 8(1) 3(1)
C(4) 20(1) 24(1) 26(1) 9(1) 9(1) 5(1)
C(5) 22(1) 24(1) 34(1) 12(1) 9(1) 4(1)
C(6) 31(1) 25(1) 38(1) 7(1) 17(1) 4(1)
C(7) 21(1) 30(1) 21(1) 10(1) 4(1) -3(1)
N(3) 21(1) 27(1) 26(1) 13(1) 9(1) 6(1)
N(4) 19(1) 23(1) 23(1) 7(1) 8(1) 6(1)
C(8) 21(1) 29(1) 32(1) 9(1) 13(1) 6(1)
C(9) 21(1) 27(1) 35(1) 12(1) 8(1) 6(1)
C(10) 23(1) 29(1) 26(1) 12(1) 7(1) 4(1)
C(11) 18(1) 23(1) 24(1) 6(1) 7(1) 2(1)
C(12) 20(1) 26(1) 25(1) 4(1) 7(1) 4(1)
C(13) 30(1) 28(1) 44(1) 10(1) 19(1) 5(1)
C(14) 25(1) 32(1) 23(1) 10(1) 10(1) 13(1)

 

211

Table Al.5 Hydrogen coordinates (>< 104) and isotropic displacement parameters
(A2 X 103) for Hzenp

 

 

x y z U(eq)
H( 1) 636 2841 6432 32
H(IA) -1923 1072 5425 38
H(2) 2995 708 2656 37
H(3) -957 2309 2017 33
H(SA) 1805 4285 3650 31
H(SB) 1822 5059 5418 31
H(6A) 2697 1259 3757 46
H(6B) 4624 1802 41 90 46
H(6C) 3386 2272 2912 46
H(7A) 5 803 4281 6039 29
H(7B) 4675 5584 6471 29
H(3A) 3797 3015 7148 28
H(8) 5902 1358 6874 32
H(9) 6772 807 9306 33
H(10) 5090 2200 I 1048 30
H(12A) 2926 4176 10889 29
H(I2B) 3188 5050 9759 29
H(13A) 689 2233 10137 49
H(13B) 1080 1225 8580 49
H(13C) -667 1797 8513 49
H(14A) -1011 4287 8446 30
H(14B) 543 5572 8955 30

 

Table Al.6 Torsion angles (°) for Hzenp

 

C(4)-N(1)-C(1)-C(2)
N(1)-C(1)-C(2)-C(3)
C(1)-C(2)-C(3)-C(4)
C(1)-N(1)-C(4)-C(3)
C(1)-N(1)-C(4)-C(5)
C(2)-C(3)-C(4)-N(1)
C(2)-C(3)-C(4)-C(5)
C(6)-N(2)-C(5)-C(4)
C(7)-N(2l-C(5)-C(4)
N(l)-C(4)-C(5)—N(2)
C(3)-C(4)-C(5)—N(2)
C(6)-N(2)-C(7)-C(7)#1
C(5)-N(2)-C(7)-C(7)#1
C(1 1)-N(3)-C(8)-C(9)
N(3)-C(8)—C(9)-C(10)
C(8)-C(9)-C(10)-C(1 1)
C(8)-N(3)-C(1 1)-C(10)
C(8)-N(3)-C(1 1)-C(12)
C(9)-C(10)-C(1 1)-N(3)
C(9)-C(10)-C(1 1 )-C(12)
C(13)-N(4)—C(12)-C(1 1)
C(14)-N(4)-C(12)-C(1 1)
N(3)-C(1 1)-C(12)-N(4)
C(10)-C(1 1)-C(12)-N(4)
C(13)-N(4)-C(14)-C(14)#2
C(12)-N(4)-C(14)-C(14)#2

—0.24(16)
0.4106)
—0.42(16)
—0.03(15)
1783702)
0.2805)
—177.96(12)
62.0804)
—170.17(10)
63.4206)
—118.58(15)
61.9808)
—64.97(18)
0.0405)
0.1005)
-0.2005)
—0.1705)
176.0201)
023(15)
—175.57(13)
65.5104)
-166.86(10)
65.2606)
—119.50(15)
62.8909)
—63.89(19)

 

Table Al.7 Hydrogen bonds (A) angles (°) for Hzenp

 

 

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
N(1)-H(1)...N(4) 0.88 2.13 2.960605) 156.7
N(3)-H(3A)...N(2) 0.88 2.12 2.945005) 156.6

 

214

Table A2.1 Crystal data for Ti(bap)(NMe2)3 (28)

Identification code
Empirical formula

Formula weight
Temperature

Wavelength

Crystal system, Space group

Unit cell dimensions

Volume
Z, Calculated density

Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Limiting indices

Reflections collected / unique

Completeness to theta = 23.28

Absorption correction

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2
Final R indices [I>2sigma(l)]
R indices (all data)

Largest diff. peak and hole

sbllt

C16 H36 N6 Ti

360.41

446(2) K

0.71073 A

Monoclinic, P2(1)/c

a = 9.3023(11) A alpha = 90°

b = 11.190704) A beta = 93.075(3)°
c = 19.610(2) A gamma = 90°
2038.4(4) A3

4, 1.174 Mg/m3

0.429 mm-1
784

0.32 x 0.68 x 0.71 mm

2.08 to 23.28 deg.
—10<=h<=10, —12<=k<=12, —21<=1<=21
17217 / 2937 [R(int) = 0.0782]

99.9 %

None

Full-matrix least-squares on F3

2937 / 0 / 208

1.049
R1 = 0.0592, wR2 = 0.1566
R1 = 0.0894, wR2 = 0.1718

0.543 and —0.474 e.A-3

215

Table A2.2 Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Ti(bap)(NMe2)3. U(eq) is defined as one third of the trace of

the orthogonalized Uij tensor

 

 

x y Z U(CQ)
Ti 2808(1) 8439(1) 8492(1) 23(1)
N( 1) 2428(4) 673 7(3) 8030(2) 26(1)
C(32) 1536(7) 8458(6) 9865(3) 56(2)
C(11) 1968(5) 6683(4) 7352(2) 25(1)
N(l 1) 2325(4) 8824(4) 7363(2) 26(1)
N(4) 3007(4) 10153(4) 8674(2) 32(1)
N(2) 4745(4) 8088(4) 8808(2) 29(1)
N(14) 2153(4) 5233(4) 9445(2) 29(1)
C(14) 2714(5) 5581(4) 8231(2) 25(1)
C(141) 3269(5) 5291(5) 8942(2) 30(1)
N(3) 1393(4) 8229(4) 9142(2) 33(1)
C(1 13) 3762(5) 8843(5) 7073(3) 34(1)
C(1 12) 1599(6) 9984(5) 7204(3) 36(1)
C(22) 5461 (6) 8570(5) 9424(3) 52(2)
C(1] 1) 1465(5) 7831(4) 7041(2) 32(1)
C(13) 2464(5) 4824(5) 7686(3) 33(1)
C(42) 1845(6) 10916(5) 8875(3) 47(2)
C(142) 1286(6) 4171(5) 9336(3) 47(2)
C(41) 4254(6) 10880(5) 853 8(3) 46(2)
C(143) 2839(7) 5214(6) 10128(3) 54(2)
C(12) 1980(5) 5530(5) 7120(3) 34(1)
C(31) 1 1(6) 7685(5) 8942(3) 47(2)
C(21) 5739(5) 7353(5) 8442(3) 33(1)

 

216

Table A2.3 Bond lengths (A) and angles (°) for Ti(bap)(NMe2)3

 

Ti-N(3) 1.894(4)
Ti-N(2) 1.915(4)
Ti-N(4) 1.958(4)
Ti-N(1) 2.131(4)
Ti-N(11) 2.277(4)
N(l)-C(l4) 1.374(6)
N(l)-C(11) 1.375(6)
C(32)—N(3) 1.440(7)
C(11)-C(12) 1.368(7)
C(11)-C(1 11) 1.487(7)
N(l l)-C(1 13) 1.480(6)
N(11)-C(1 12) 1.488(6)
N(l 1 )-C(1 1 1) 1.490(6)
N(4)-C(42) 1.448(7)
N(4)-C(41) 1.454(7)
N(2)-C(22) 1.452(6)
N(2)-C(21) 1.455(6)
N(l4)—C(142) 1.445(6)
N(14)-C(143) 1.451(6)
N(14)-C(14l) 1.471(6)
C(14)-C(13) 1.373(7)
C(14)-C(141) 1.497(7)
N(3)-C(31) 1.457(7)
C(13)-C(12) 1.415(7)
N(3)-Ti-N(2) 1 15.6608)
N(3)-Ti-N(4) 93.5207)
N(2)-Ti-N(4) 93.6507)
N(3)-Ti-N(1) 94.0106)

217

N(2)-Ti-N(l) 94.9506)
N(4)-Ti-N(1) 164.8106)
N(3)-Ti-N(11) 124.730 7)
N(2)—Ti-N(1 1) 119.080 6)
N(4)-Ti-N(11) 90.1906)
N(1)-Ti-N(1 1) 74.6804)
C(14)-N(l)-C(1 1) 106.3(4)
C(14)-N(1)—Ti 134.0(3)
C(1 1)-N(1)-Ti 119.1(3)
C(12)-C(1 1)-N(1) 110.8(4)
C(12)-C(11)-C(111) 133.3(4)
N(1)-C(11)-C(111) 115.6(4)
C(113)-N(l 1)-C(112) 108.4(4)
C(113)-N(11)-C(111) 108.9(4)
C(1 12)-N(11)-C(111) 109.5(4)
C(1 13)-N(1 1)-Ti 104.0(3)
C(1 12)-N(1 1)-Ti 115.6(3)
C(111)-N(11)-Ti 110.1(3)
C(42)-N(4)-C(41) 109.5(4)
C(42)-N(4)-Ti 124.2(3)
C(41)—N(4)-Ti 125.7(3)
C(22)-N(2)-C(21) 1 10.2(4)
C(22)-N(2)-Ti 125.1(3)
C(21)-N(2)—Ti 124.6(3)
C(142)-N(14)-C(143) 109.8(4)
C(142)-N(14)-C(141) 110.1(4)
C(143)-N(14)-C(l4l) 109.1(4)
C(13)-C(14)-N(l) 109.6(4)
C(13)-C(14)-C(141) 128.8(5)
N(1)-C(14)-C(141) 121.5(4)
N(14)-C(141)-C(14) 114.4(4)

C(32)-N(3)-C(31) 1 1 1.8(4)

C(32)-N(3)-Ti 127.6(4)
C(31)-N(3)-Ti 120.4(3)
C(11)-C(111)-N(11) 108.7(4)
C(14)-C(13)-C(12) 107.4(5)
C(11)-C(12)-C(13) 105.9(4)

 

Table A2.4 Anisotropic displacement parameters (A2 X 103) for Ti(bap)(NMe2)3. The

anisotropic displacement factor exponent takes the form: —2 pi2 [ h2 a"‘2 U11 + + 2 h k
a* bat: U12 ]

 

 

1111 1122 1133 1123 1113 1112
Ti 24(1) 26(1) 21(1) 0(1) 3(1) 1(1)
N(l) 23(2) 31(3) 25(2) 1(2) 1(2) -1(2)
C(32) 62(4) 67(4) 41(4) -6(3) 21(3) -3(4)
C(11) 21(3) 37(3) 18(3) 2(2) 1(2) -2(2)
N(l 1) 24(2) 30(2) 25(2) 4(2) 1(2) -1(2)
N(4) 32(2) 26(2) 36(2) 0(2) 6(2) -2(2)
N(2) 27(2) 32(2) 26(2) -4(2) -3(2) 0(2)
N(14) 35(2) 27(2) 25(2) 5(2) —3(2) 1(2)
C(14) 20(3) 28(3) 27(3) 0(2) 1(2) 0(2)
C041) 25(3) 31(3) 34(3) 5(2) -1(2) 1(2)
N(3) 34(3) 30(2) 35(3) 0(2) 1 1(2) 1(2)
C013) 29(3) 43(3) 31(3) 6(2) 5(2) 1(2)
C012) 36(3) 40(3) 32(3) 9(3) 1(2) 7(3)
C(22) 51(4) 52(4) 50(4) -16(3) -16(3) 7(3)
C011) 28(3) 41(3) 26(3) 1(2) —2(2) -3(2)
C(13) 29(3) 32(3) 38(3) -7(3) 7(2) -1(2)

219

C(42)

C(142)

C(41)

C(143)

C(12)
C(31)
C(21)

51(4)
50(4)
55(4)
56(4)
33(3)
34(3)
27(3)

35(3)
44(4)
38(3)
73(5)
43(3)
56(4)
40(3)

54(4)
48(4)
46(4)
32(3)
24(3)
51(4)
33(3)

-4(3)
3(3)
2(3)
5(3)

-9(3)

1 1(3)
4(3)

-1(3)
5(3)
2(3)
-2(3)
4(2)
13(3)
3(2)

12(3)

-16(3)
-11(3)

1(3)
-5(3)
7(3)
3(2)

 

Table A2.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X

 

 

220

103) for Ti(bap)(NMe2)3
x y z U(eq)
H(32A) 646 8272 10068 84
H(3213) 1765 9285 9941 84
H(32C) 2291 7969 10068 84
H(14A) 3762 4527 8936 36
H(14B) 971 5891 9089 36
H0 1A) 3656 9003 6592 51
H0 113) 4222 8083 7146 51
H(l 1C) 4340 9458 7292 51
H(l 11)) 1440 10064 6719 54
H(l 1E) 2196 10628 7376 54
H0 1F) 692 10007 7415 54
H(22A) 6426 8265 9471 78
H(22B) 4943 8338 9813 78
H(22C) 5488 9426 9395 78
H(l 1(1) 452 7947 7115 38
H01H) 1586 7818 6553 38

1u13A)
IK42A)
FK4ZB)
H(42C)
EH14C)
rK14E»
1K14E)
1H41A)
FK41B)
EH41C)
IK14F)
hul4cn
PK14PD
H(12A)
1H31A)
FK3IB)
EH31c»
1H21A)
1K21B)
PKZIC)

2590
2194
1492
1081
558
1888
838
4083
4417
5084
2115
3397
3457
1723
-572
I65
-469
6645
5880
5347

4000

11718
10631
10904

4145
3476
4187

11691
10856
10575

5173
5929
4530
5265
7648
6892
8157
7309
7701
6564

7688
8935
9296
8526
9664
9387
8883
8672
8059
8792

10458
10201
10176

6681
9331
8774
8590
8699
8003
8382

39
70
70
70
71
71
71
69
69
69

81
81
40
70
70
70
50
50
50

 

1x)
Ix)

Table A3.1 Crystal data for Ti(NNMe2)(dap)(nacnac) (36)

Identification code
Empirical formula

Formula weight
Temperature

Wavelength

Crystal system, space group

Unit cell dimensions

Volume
Z, Calculated density

Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Limiting indices

Reflections collected / unique

Completeness to theta = 23.33
Absorption correction

Max. and min. transmission

Refinement method

Data / restraints / parameters
Goodness-of-fit on F 2

Final R indices [I>23igma(l)]
R indices (all data)

Extinction coefficient

Largest diff. peak and hole

sb2t

C22 H43 N7 Ti

453.53

446(2) K

0.71073 A

Monoclinic, P2(1)/c
a = 9.1796(14) A alpha = 90 deg.
b = 19.161(3) A beta = 102.598(3) deg.
c = 15.043(2) A gamma = 90 deg.
2582.3(7) A3
4, 1.167 Mg/m3

0.353 mm‘1

984

0.42 X 0.45 X 0.54 mm

1.75 to 23.33 deg.

-10<=h<=10, -21<=k<=21, —16<=1<=16
22066 / 3737 [R(int) = 0.1467]
99.7 %

Empirical

0.2484 and 0.1016

Full-matrix least-squares on F2

3737 / 0 / 272

1.012

R1 = 0.0436, wR2 = 0.1040
R1 = 0.0742, wR2 = 0.1300
0.019908)

0.414 and —0.398 e. A-3

Table A3.2 Atomic coordinates ( X 104) and equivalent isotropic displacement

parameters (A2 X 103) for Ti(NNMe2)(dap)(nacnac). U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor

 

 

x y z U(eq)
Ti 1167(1) 6109(1) 2069(1) 28(1)
N(l) 2126(3) 5174(1) 1708(2) 34(1)
N(2) 2461(3) 6550(1) 2859(2) 34(1)
N(3) -37(3) 5533(1) 2834(2) 28(1)
N(4) -799(3) 663 8(1) 1609(2) 30(1)
N(ll) 2128(3) 6396(1) 810(2) 35(1)
N(21) 3629(3) 6791(2) 3555(2) 46(1)
N(31) 190(3) 5362(1) 3798(2) 33(1)
C(1) -4943(4) 4169(2) 3948(2) 54(1)
C(2) -3660(4) 4044(2) 3488(2) 40(1)
C(3) -3147(3) 4699(2) 3081(2) 31(1)
C(4) -1852(3) 4551(2) 2624(2) 32(1)
C(5) -1 159(3) 5192(2) 2302(2) 28(1)
C(6) -1758(3) 5459(2) 1420(2) 32(1)
C(7) -1735(4) 6153(2) 1173(2) 34(1)
C(1 1) 1996(4) 4468(2) 1831(2) 38(1)
C(12) 2941(4) 4103(2) 1417(2) 44(1)
C(13) 3704(4) 4601(2) 998(2) 43(1)
C(14) 3180(3) 5241(2) 1187(2) 35(1)
C(15) 3513(4) 5970(2) 943(2) 41(1)
C(40) -1380(4) 7375(2) 1557(2) 39(1)
C(41) -177(4) 7825(2) 2134(3) 52(1)
C(42) -2759(4) 7392(2) 1976(3) 54(1)
C(43) -1777(5) 7647(2) 579(3) 61(1)
C(1 1 1) 1083(4) 6180(2) -44(2) 47(1)
C(112) 2518(4) 7140(2) 736(3) 50(1)

C(211)
C(212)
C(311)
C(312)

4977(4)
3912(4)
1708(4)
-41(4)

6364(2)
7525(2)
5106(2)
6007(2)

3606(3)
3475(3)
4120(2)
4266(2)

52(1)
55(1)
47(1)
49(1)

 

 

Ti-N(2)
Ti-N(4)
Ti-N(3)
Ti-N(1)

Ti-N(1 1)

Ti-C(7)

N(1)-C(1 1)
N(l)-C(l4)
N(2)-N(21)

N(3)-C(5)

N(3)-N(31)

N(4)-C(7)

N(4)-C(40)
N(11)-C(112)
N(ll)-C(111)
N(l 1)-C(15)
N(21)-C(212)
N(21)-C(21 1)
N(31)-C(31 1)
N(31)-C(312)

C(1)-C(2)

1.709(3)
2.055(3)
2.077(2)
2.1 19(3)
2.323(3)
2.713(3)
1.373(4)
1.377(4)
1.403(4)
1.330(4)
1.457(3)
1.337(4)
1.504(4)
1.480(4)
1.485(4)
1.487(4)
1.440(4)
1.471(4)
1.457(4)
1.460(4)
1.510(4)

224

Table A3.3 Bond lengths (A) and angles (°) for Ti(NNMe2)(dap)(nacnac)

C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(1 1)-C(12)
C(12)-C(13)
C(13)-C(14)
C(14)-C(15)
C(40)-C(41)
C(40)-C(43)
C(40)-C(42)

N(2)-Ti-N(4)
N(2)-Ti-N(3)
N(4)-Ti-N(3)
N(2)-Ti-N(1)
N(4)-Ti-N(1)
N(3)-Ti-N(1)
N(2)-Ti-N(1 1)
N(4)-Ti-N(1 1)
N(3)-Ti-N(1 1)
N(1)-Ti-N(1 1)
N(2)-Ti-C(7)
N(4)-Ti-C(7)
N(3)-Ti-C(7)
N(1)-Ti-C(7)
N(l l)-Ti-C(7)
C(11)-N(1)-C(14)
C(1 1)-N(1)-Ti
C(14)-N(1)-Ti

1.516(4)
1.524(4)
1.510(4)
1.418(4)
1.382(4)
1.366(4)
1.41 1(5)
1.370(4)
1.493(4)
1.516(5)
1.529(5)
1.533(5)

1 14.6102)
104.5101)
85.0800)
109.3801)
135.6100)
89.65(10)
96.89(11)
94.0200)
156.8600)
74.8300)
142.0401)
2853(9)
73.0500)
108.4800)
9536(9)
105.2(3)
138.1(2)
1 16.7(2)

N(21)-N(2)—Ti 169.6(2)
C(5)-N(3)-N(31) 1 14.3(2)
C(5)-N(3)-Ti 11 1.3509)
N(31)-N(3)-Ti 133.8609)
C(7)-N(4)-C(40) 1 16.4(3)
C(7)-N(4)-Ti 104.2(2)
C(40)-N(4)-Ti 139.1(2)
C(112)-N(11)-C(111) 109.0(3)
C(112)-N(1 l)-C(15) 108.9(3)
C(1] 1)-N(1 1)-C(15) 109.6(2)
C(112)-N(11)-Ti 115.5109)
C(111)—N(11)-Ti 110.5509)
C(15)-N(11)-Ti 103.050 8)
N(2)-N(21)-C(212) 112.4(3)
N(2)-N(21)-C(21 1) 110.7(3)
C(212)-N(21)-C(21 1) 1 12.5(3)
N(3)-N(31)-C(31 1) 109.0(2)
N(3)-N(3l)-C(312) 106.6(2)
C(311)-N(31)-C(312) 110.7(3)
C(1)-C(2)-C(3) 113.3(3)
C(2)-C(3)-C(4) 1 1 1.7(3)
C(5)-C(4)-C(3) 1 14.8(2)
N(3)-C(5)-C(6) 1 18.5(3)
N(3)-C(5)-C(4) 122.1(3)
C(6)-C(5)-C(4) 1 19.3(3)
C(7)-C(6)-C(5) 125.0(3)
N(4)-C(7)-C(6) 125.6(3)
N(4)-C(7)-Ti 47.2405)
C(6)-C(7)-Ti 84.6709)
C(12)-C(11)-N(1) 111.1(3)
C(11)-C(12)-C(13) 106.5(3)

226

C(14)-C(13)-C(12)
C(13)-C(14)-N(1)
C(13)-C(14)-C(15)
N(l)-C(l4)-C(15)
N(l 1)-C(15)-C(14)
N(4)-C(40)-C(41)
N(4)-C(40)-C(43)
C(41)-C(40)-C(43)
N(4)-C(40)-C(42)
C(41)-C(40)-C(42)
C(43)-C(40)-C(42)

106.3(3)
110.9(3)
133.4(3)
115.8(3)
109.4(3)
107.4(3)
112.2(3)
110.3(3)
108.3(3)
108.4(3)
110.1(3)

 

Table A3.4 Anisotropic displacement parameters (A2 X 103) for Ti(NNMe2)(dap)
(nacnac). The anisotropic displacement factor exponent takes the form:

—2pi2[h2a*21111+...+2hka*b*1112]

 

 

1111 1122 U33 U23 1113 1112
Ti 29(1) 31(1) 25(1) -10) 7(1) -10)
N(l) 34(2) 37(2) 32(2) 0(1) 7(1) 1(1)
N(2) 31(2) 36(2) 33(2) -3(1) 6(1) -50)
N(3) 29(2) 31(2) 23(2) 1(1) 4(1) 0(1)
N(4) 32(2) 29(2) 31(2) 2(1) 8(1) -30)
N(ll) 37(2) 40(2) 30(2) -10) 12(1) -20)
N(21) 40(2) 53(2) 43(2) -9(2) 2(2) -10(2)
N(31) 33(2) 46(2) 20(2) 4(1) 6(1) 2(1)
C(1) 44(2) 75(3) 44(2) 4(2) 14(2) -17(2)
C(2) 39(2) 43(2) 40(2) -1(2) 10(2) -7(2)
C(3) 29(2) 35(2) 28(2) 0(2) 1(2) 2(1)
C(4) 36(2) 28(2) 33(2) -3(2) 7(2) -1(2)

C(5)

C(6)

C(7)

C(11)
C(12)
C(13)
C(14)
C(15)
C(40)
C(41)
C(42)
C(43)

C011)
C012)
C(211)
C(212)
C(311)
C(312)

28(2)
37(2)
35(2)
45(2)
52(2)
35(2)
27(2)
37(2)
36(2)
47(2)
43(2)
65(3)

55(2)
64(3)
36(2)
61(3)
37(2)
61(3)

30(2)
33(2)
41(2)
37(2)
40(2)
61(2)
50(2)
55(2)
29(2)
31(2)
41(2)
49(2)

57(2)
45(2)
68(3)
49(2)
69(3)
56(2)

28(2)
23(2)
24(2)
31(2)
35(2)
30(2)
29(2)
34(2)
52(2)
81(3)
82(3)
68(3)

30(2)
50(2)
50(2)
52(3)
31(2)
30(2)

412)
-4(2)

5(2)
0(2)
-7(2)
-9(2)
-6(2)
-6(2)
7(2)
-9(2)
2(2)
22(2)
1(2)
2(2)
0(2)

44(2)
15(2)
-9(2)

1 1(2)
2(2)
4(2)
5(2)
-1(2)
4(2)
4(2)
17(2)
1 1(2)
21(2)
24(2)
12(2)
13(2)
32(2)
3(2)
6(2)
2(2)
15(2)

3(1)

4(2)

1(2)
3(2)
12(2)
13(2)
2(2)
-6(2)
3(2)
-2(2)
2(2)
10(2)
-1 (2)
-10(2)
-5(2)
44(2)
1(2)
-7(2)

 

Table A3.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X

103) for Ti(NNMe2)(dap)(nacnac)

 

 

x y z U(eq)
H(1A) -5217 3737 4191 81
H03) -5781 4350 3513 81
H(lC) -4646 4500 4434 81
H(2A) -3961 3701 3009 48
H(2B) -2827 3851 3929 48

FK3A0

FK3B)

1H4A0

EK4B)

EH6A)

1H7A)

FKIIAJ
rule)
1H13A)
1H1sA)
1H1SB)
1H41A)
EK4IB)
1u41c»
1H4zA)
H(42B)
H(42C)
H(43A)
H(43B)
H(43C)
EKIIB)
1x111»
11(111»
PKIIE)
PKIIF)
PK11CD
1H21A)
FKZIB)
1H21c»
PKZIED
PKZIE)

-2840
-3974
-1085
-2203
-2201
-2431
1350
3058
4421
4274
3887
696
70
-535
-2498
-3527
-3114
-907
-2130
-2543
1496
144
934
2903
3262
1643
4735
5725
5352
3004
4274

5043
4893
4301
4248
5143
6295
4266
3621
4513
6171
5969
7820
7646
8295
7221
7104
7863
7635
8119
7360
6302
6413
5684
7208
7273
7422
5881
6501
6432
7781

7607

229

38
38
39
39
38
41
46
53
51
49
49
78
78
78
81
81
81
92
92
92
70
70
70
76
76
76
78
78
78
83
83

H(21F)
H(31A)
H(31B)
H(31C)
H(3 1 D)
H(31E)
H(3 1 F)

4647
1839
1882
2403

-1046
645
125

7676
4684
5015
5452
6167
6356
5921

3995
3804
4762
4006
4046
4152

4909

83
70
70
70
73
73
73

 

230

Table A4.1 Crystal data for Ti2(dap)3(NNMe2)2(NHNMe2) (37)

Identification code
Empirical formula

Formula weight
Temperature
Wavelength
Crystal system
Space group

Unit cell dimensions

Volume

Z
Density (calculated)

Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected
Independent reflections
Completeness to theta = 25.00°
Absorption correction

Max. and min. transmission

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2
Final R indices [I>2sigma(l)]
R indices (all data)

sbfinal

C28 H54 C12 N12 Tiz

725.53

173(2) K

0.71073 A

Monoclinic

P 21/n

a=11.9144(3)A a= 90°.
b = 9.9855(3) A b= 93.951(2)°.
c = 30.2370(9) A g = 90°.
35887808) A3

4

1.343 Mg/m3

0.632 mm-1
1536

0.26 x 0.18 x014 mm3

1.80 to 25.39°.

-14<=h<=14, -9<=k<=12, —36<=l<=36
42331

6579 [R(int) = 0.0376]

100.0 %

Semi-empirical from equivalents

0.9162 and 0.8530

Full-matrix least-squares on F2

6579 / 0 / 409

1.031
R1 = 0.0334, wR2 = 0.0782
R1 = 0.0449, wR2 = 0.0840

231

Largest diff. peak and hole 0.508 and -0.489 e.A"3

Table A4.2 Atomic coordinates ( X 104) and equivalent isotropic displacement
parameters (A2 X 103) for sbfinal. U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor

 

 

x y z U(eq)
Ti(l) 10152(1) 2884(1) 1459(1) 17(1)
Ti(2) 8010(1) 1758(1) 1306(1) 17(1)
N(l) 11129(1) 1347(2) 1222(1) 22(1)
N(2) 11578(1) 2361(2) 2052(1) 24(1)
N(3) 10214(l) 4753(2) 1774(1) 21(1)
N(4) 1 1292(1) 4449(2) 1010(1) 26(1)
N(5) 9179(1) 1957(2) 1795(1) 18(1)
N(6) 8354(1) 1249(2) 2008(1) 21(1)
N(7) 9058(1) 2918(2) 993(1) 19(1)
N(8) 8192(1) 2771(2) 658(1) 22(1)
N(9) 6943(1) 3341(2) 1476(1) 22(1)
N(10) 6151(1) 884(2) 1242(1) 25(1)
N(l 1) 8472(1) 27(2) 1070(1) 23(1)
N(12) 8059(2) -1217(2) 886(1) 27(1)
C(29) 1 1292(2) 842(2) 808(1) 30(1)
C(30) 12077(2) -159(2) 836(1) 38(1)
C(31) 12433(2) -301(2) 1289(1) 36(1)
C(32) 11836(2) 619(2) 1514(1) 25(1)
C(33) 1 1779(2) 908(2) 1993(1) 28(1)
C(34) 11216(2) 2607(3) 2503(1) 33(1)
C(35) l2647(2) 3083(2) 201 1(1) 32(1)

232

C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C10)
C1(2)
C(56)

9647(2)
9972(2)
10789(2)
10919(2)
1 1724(2)
10494(2)
12243(2)
7881(2)
8745(2)
8561(2)
7619(2)
7136(2)
6144(2)
5281(2)
5795(2)
5379(2)
5811(2)
6016(2)
8429(2)
8490(2)
4135(1)
5747(1)
5460(2)

5248(2)
6536(2)
6879(2)
5779(2)
5527(2)
5066(2)
3907(3)
2013(2)

-88(2)
2056(2)
4028(2)
4689(2)
5362(2)
4393(2)
3182(2)
1781(2)

863(3)
-478(2)

4413(3)
2309(2)

7291(1)
6659(1)
6622(3)

2120(1)
2220(1)
1922(1)
1661(1)
1314(1)
678(1)
774(1)
2368(1)
2162(1)
266(1)
514(1)
1540(1)
1566(1)
1520(1)
1468(1)
1471(1)
763(1)
1425(1)
440(1)
1170(1)
631(1)
-190)
539(1)

23(1)
26(1)
26(1)
22(1)
27(1)
36(1)
40(1)
29(1)
29(1)
32(1)
29(1)
23(1)
28(1)
35(1)
27(1)
34(1)
37(1)
34(1)
42(1)
42(1)
55(1)
66(1)
52(1)

 

Table A4.3 Bond lengths (A) and angles (°) for T12(dap)3(NNMe2)2(NHNMe2)

 

Ti(l )-N(5) 1.84250 5)
Ti(1)-N(7) 1.851606)
Ti(1)-N(1) 2.083306)

233

Ti(l)-N(3)
Ti(1)-N(2)
Ti(1)-N(4)
Ti(1)-Ti(2)
Ti(2)-N(l 1)
Ti(2)-N(5)
Ti(2)-N(7)
Ti(2)-N(9)
Ti(2)-N(6)
Ti(2)-N(8)
Ti(2)-N(10)
N(1)-C(29)
N(l)-C(32)
N(2)-C(35)
N(2)-C(34)
N(2)-C(33)
N(3)-C(36)
N(3)-C(39)
N(4)-C(41)
N(4)-C(42)
N(4)-C(40)
N(5)-N(6)
N(6)-C(43)
N(6)-C(44)
N(7)-N(8)
N(8)-C(45)
N(8)-C(46)
N(9)-C(50)
N(9)-C(47)

N(10)-C(52)
N(10)-C(53)

2.093607)
2.439907)
2.5259(17)
2.7971(5)
1.9631(17)
1.970706)
1.988806)
2.1 1500 7)
2.193707)
2.228607)
2.376807)
1.376(3)
1.382(3)
1.477(3)
1.480(3)
1.483(3)
1.376(2)
1.383(3)
1.472(3)
1.483(3)
1.484(3)
1.402(2)
1.475(3)
1.479(3)
1.404(2)
1.475(3)
1.480(3)
1.375(3)
1.377(3)
1.479(3)
1.481(3)

234

N(10)-C(51)
N(l 1)-N(12)
N(11)-H(1 1)
N(12)-C(55)
N(12)-C(54)
C(29)-C(30)
C(29)-H(29)
C(30)-C(31)
C(30)-H(30)
C(31)-C(32)
C(31)-H(31)
C(32)-C(33)
C(33)-H(33A)
C(33)-H(33B)
C(34)-H(34A)
C(34)-H(34B)
C(34)-H(34C)
C(35)-H(35A)
C(35)-H(3SB)
C(35)-H(35C)
C(36)-C(37)
C(36)-H(36)
C(37)-C(38)
C(37)-H(37)
C(38)-C(39)
C(38)-H(38)
C(39)-C(40)
C(40)-H(40A)
C(40)-H(4OB)
C(41)-H(41A)
C(41)-H(4IB)

1.488(3)
1.434(2)
0.8800
1.458(3)
1.461(3)
1.367(3)
0.9500
1.414(3)
0.9500
1.371(3)
0.9500
1.485(3)
0.9900
0.9900
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.370(3)
0.9500
1.414(3)
0.9500
1.367(3)
0.9500
1.491(3)
0.9900
0.9900
0.9800
0.9800

235

C(41)-H(41C)
C(42)-H(42A)
C(42)-H(4ZB)
C(42)-H(42C)
C(43)-H(43A)
C(43)-H(43B)
C(43)-H(43C)
C(44)-H(44A)
C(44)-H(44B)
C(44)-H(44C)
C(45)-H(45A)
C(45)-H(45B)
C(45)-H(45C)
C(46)-H(46A)
C(46)-H(46B)
C(46)-H(46C)
C(47)-C(48)

C(47)-H(47)

C(48)-C(49)

C(48)-H(48)

C(49)-C(50)

C(49)-H(49)

C(50)-C(51)

C(51)-H(51A)
C(51)-H(51B)
C(52)-H(52A)
C(52)-H(SZB)
C(52)-H(52C)
C(53)-H(53A)
C(53)-H(53B)
C(53)-H(53C)

0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.367(3)
0.9500
1.412(3)
0.9500
1.369(3)
0.9500
1.485(3)
0.9900
0.9900
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800

236

C(54)-H(54A)
C(54)-H(54B)
C(54)-H(54C)
C(55)-H(55A)
C(55)-H(SSB)
C(55)-H(55C)
C10)-C(56)

C1(2)-C(56)

C(56)-H(56A)
C(56)-H(56B)

N(5)-Ti(1)-N(7)
N(5)-Ti(1)-N(1)
N(7)-Ti(1)-N(l)
N(5)-Ti(1)-N(3)
N(7)-Ti(1)-N(3)
N(1)-Ti(l)-N(3)
N(5)-Ti(1)-N(2)
N(7)-Ti(1)-N(2)
N(1)-Ti(1)—N(2)
N(3)-Ti(1)-N(2)
N(5)-Ti(1)-N(4)
N(7)-Ti(1)-N(4)
N(1)-Ti(1)-N(4)
N(3)-Ti(l)—N(4)
N(2)-Ti(l)—N(4)
N(5)-Ti(l)—Ti(2)
N(7)-Ti(l)—Ti(2)
N(1)—Ti(1)-Ti(2)
N(3)-Ti(1)-Ti(2)
N(2)-Ti(1)-Ti(2)

0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.753(3)
1.744(3)
0.9900
0.9900

8957(7)
101.95(7)
9765(7)
101.58(7)
109.32(7)
144.05(7)
8540(6)
168.66(7)
7356(6)
81.69(6)
171.46(7)
8751(6)
8640(6)
7191(6)
9885(6)
4463(5)
4521(5)
9991(5)
1 1592(5)
128.07(4)

237

N(4)-Ti(l)—Ti(2) 132.68(4)
N(l 1)—Ti(2)—N(5) 9922(7)
N(l 1)-Ti(2)-N(7) 9803(7)
N(5)-Ti(2)-N(7) 8218(6)
N(l 1)-Ti(2)-N(9) 159.23(7)
N(5)-Ti(2)-N(9) 9845(7)
N(7)-Ti(2)-N(9) 9509(7)
N(l 1)-Ti(2)-N(6) 9624(7)
N(5)-Ti(2)-N(6) 3889(6)
N(7)-Ti(2)-N(6) 120.88(6)
N(9)-Ti(2)-N(6) 9071(6)
N(l 1)-Ti(2)-N(8) 9196(7)
N(5)-Ti(2)-N(8) 120.53(6)
N(7)—Ti(2)-N(8) 3836(6)
N(9)-Ti(2)-N(8) 8838(6)
N(6)-Ti(2)-N(8) 158.89(6)
N(l 1)-Ti(2)-N(10) 8600(6)
N(5)-Ti(2)-N(10) 134.74(6)
N(7)-Ti(2)-N(10) 141.99(7)
N(9)-Ti(2)-N(10) 7380(6)
N(6)-Ti(2)-N(10) 9595(6)
N(8)-Ti(2)-N(10) 104.02(6)
N0 1)-Ti(2)-Ti(1) 9798(5)
N(5)-Ti(2)-Ti(1) 4106(4)
N(7)-Ti(2)—Ti(1) 4136(5)
N(9)-Ti(2)-Ti(1) 102.49(5)
N(6)-Ti(2)-Ti(1) 7995(4)
N(8)-Ti(2)-Ti(1) 7966(4)
N(10)-Ti(2)-Ti(1) 174.53(4)
C(29)-N(1)-C(32) 105.6507)
C(29)-N(l)-Ti(1) 134.3805)

238

C(32)-N(1)-Ti(l)
C(35)-N(2)-C(34)
C(35)-N(2)-C(33)
C(34)-N(2)-C(33)
C(35)-N(2)-Ti(1)
C(34)-N(2)-Ti(1)
C(33)-N(2)-Ti(1)
C(36)-N(3)-C(39)
C(36)-N(3)-Ti(1)
C(39)-N(3)-Ti(1)
C(41)-N(4)-C(42)
C(41)-N(4)-C(40)
C(42)-N(4)-C(40)
C(41)-N(4)-Ti(1)
C(42)-N(4)-Ti(l)
C(40)-N(4)-Ti(l)
N(6)-N(5)-Ti(1)
N(6)-N(5)-Ti(2)
Ti(l)—N(5)-Ti(2)
N(5)-N(6)-C(43)
N(5)-N(6)-C(44)
C(43)-N(6)-C(44)
N(5)-N(6)-Ti(2)
C(43)-N(6)-Ti(2)
C(44)-N(6)-Ti(2)
N(8)-N(7)-Ti(l)
N(8)-N(7)-Ti(2)
Ti(l)—N(7)-Ti(2)
N(7)-N(8)-C(45)
N(7)-N(8)-C(46)
C(45)-N(8)-C(46)

119.9403)
107.6507)
108.6706)
109.3807)
113.3203)
114.2202)
103.4202)
105.0006)
131.4903)
123.4903)
107.5507)
107.4107)
108.62(16)
106.2602)
119.4104)
107.0501)
173.4904)
79.18(10)
9431(7)
113.1705)
112.6105)
111.2406)
6193(9)
122.6903)
123.2503)
172.3803)
80.1000)
9343(7)
112.6406)
115.1706)
109.3806)

239

N(7)-N(8)-Ti(2)
C(45)-N(8)-Ti(2)
C(46)-N(8)—Ti(2)
C(50)-N(9)—C(47)
C(50)-N(9)-Ti(2)
C(47)-N(9)-Ti(2)
C(52)-N(10)-C(53)
C(52)-N(10)-C(51)
C(53)-N(10)-C(51)
C(52)-N(10)-Ti(2)
C(53)-N(10)-Ti(2)
C(51)-N(10)-Ti(2)
N(12)-N(1 1)-Ti(2)
N(12)-N(11)-H(11)
Ti(2)-N(1 1)-H(1 1)
N(1 l)-N(12)-C(55)
N(l 1 )-N(12)-C(54)
C(55)-N(12)-C(54)
C(30)-C(29)-N(1)
C(30)-C(29)-H(29)
N(l)-C(29)-H(29)
C(29)-C(30)-C(31)
C(29)-C(30)-H(30)
C(31)-C(30)-H(30)
C(32)-C(31)-C(30)
C(32)-C(31)—H(31)
C(30)-C(31)-H(31)
C(31)-C(32)-N0)
C(31)-C(32)-C(33)
N(1)-C(32)-C(33)
N(2)-C(33)-C(32)

6153(9)
122.5103)
124.9703)
105.7907)
121.5704)
131.8103)
108.88(l7)
109.1408)
107.0306)
105.9603)
115.5803)
110.1202)
143.7203)
108.1
108.1
108.7907)
110.8807)
109.0609)
110.6(2)
124.7
124.7
106.9(2)
126.6
126.6
106.4(2)
126.8
126.8
110.5009)
132.5(2)
1169607)
1089707)

240

N(2)-C(33)-H(33A)
‘C(32)-C(33)-H(33A)
N(2)-C(33)-H(33B)
C(32)-C(33)-H(33B)
H(33A)—C(33)-H(33B)
N(2)-C(34)—H(34A)
N(2)-C(34)-H(34B)
H(34A)-C(34)-H(34B)
N(2)-C(34)-H(34C)
H(34A)—C(34)-H(34C)
H(34B)-C(34)-H(34C)
N(2)-C(35)-H(35A)
N(2)-C(35)-H(3SB)
H(35A)-C(35)-H(3SB)
N(2)-C(35)-H(35C)
H(35A)-C(35)-H(35C)
H(3SB)-C(35)-H(35C)
C(37)-C(36)-N(3)
C(37)-C(36)—H(36)
N(3)-C(36)-H(36)
C(36)-C(37)-C(38)
C(36)-C(37)-H(37)
C(38)-C(37)-H(37)
C(39)-C(38)-C(37)
C(39)-C(38)-H(38)
C(37)-C(38)-H(38)
C(38)-C(39)-N(3)
C(38)-C(39)-C(40)
N(3)-C(39)-C(40)
N(4)-C(40)-C(39)
N(4)-C(40)-H(40A)

109.9
109.9
109.9
109.9
108.3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
111.0608)
124.5
124.5
106.4708)
126.8
126.8
106.4208)
126.8
126.8
111.0407)
130.2009)
118.620 8)
110.2406)
109.6

241

C(39)-C(40)-H(40A)
N(4)-C(40)-H(4OB)
C(39)-C(40)-H(4OB)
H(40A)-C(40)-H(4OB)
N(4)-C(41)—H(41A)
N(4)-C(4I)-H(41B)
H(4lA)-C(41)-H(4IB)
N(4)-C(41)-H(41C)
H(41A)-C(41)-H(41C)
H(4lB)-C(4l)—H(41C)
N(4)-C(42)-H(42A)
N(4)-C(42)-H(4ZB)
H(42A)-C(42)-H(4ZB)
N(4)-C(42)-H(42C)
H(42A)-C(42)-H(42C)
H(4ZB)-C(42)-H(42C)
N(6)-C(43)-H(43A)
N(6)-C(43)-H(43B)
H(43A)-C(43)-H(43B)
N(6)-C(43)-H(43C)
H(43A)-C(43)-H(43C)
H(43B)-C(43)-H(43C)
N(6)-C(44)-H(44A)
N(6)-C(44)-H(44B)
H(44A)—C(44)-H(44B)
N(6)-C(44)—H(44C)
H(44A)-C(44)-H(44C)
H(44B)-C(44)-H(44C)
N(8)-C(45)-H(45A)
N(8)-C(45)-H(4SB)
H(45A)-C(4S)—H(45B)

109.6
109.6
109.6
108.1
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5

242

N(8)-C(45)-H(45C)
H(45A)-C(45)-H(45C)
H(45B)-C(45)-H(45C)
N(8)-C(46)-H(46A)
N(8)-C(46)-H(46B)
H(46A)-C(46)-H(46B)
N(8)-C(46)—H(46C)
H(46A)-C(46)-H(46C)
H(46B)-C(46)-H(46C)
C(48)-C(47)-N(9)
C(48)-C(47)-H(47)
N(9)-C(47)-H(47)
C(47)-C(48)-C(49)
C(47)-C(48)-H(48)
C(49)-C(48)-H(48)
C(50)-C(49)-C(48)
C(50)-C(49)-H(49)
C(48)-C(49)-H(49)
C(49)-C(50)-N(9)
C(49)-C(50)-C(51)
N(9)-C(50)-C(51)
C(50)-C(51)-N(10)
C(50)-C(51)-H(51A)
N(10)-C(51)-H(51A)
C(50)-C(51)-H(51B)
N(10)-C(51)-H(51B)
H(SlA)-C(51)-H(51B)
N(10)-C(52)-H(52A)
N(10)-C(52)-H(5213)
H(52A)-C(52)-H(SZB)
N(10)-C(52)-H(52C)

109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
110.600 9)
124.7
124.7
106.5009)
126.7
126.7
106.7209)
126.6
126.6
1 1039(19)
132.7709)
116.1208)
110.2907)
109.6
109.6
109.6
109.6
108.1
109.5
109.5
109.5
109.5

243

H(52A)—C(52)-H(52C)
H(52B)-C(52)-H(52C)
N(10)-C(53)-H(53A)
N(10)-C(53)-H(53B)
H(53A)-C(53)-H(53B)
N(10)-C(S3)-H(53C)
H(53A)-C(53)-H(53C)
H(53B)-C(53)-H(53C)
N(12)-C(54)-H(54A)
N(12)-C(54)-H(54B)
H(54A)-C(54)-H(54B)
N(12)-C(54)—H(54C)
H(54A)-C(54)-H(54C)
H(S4B)—C(54)-H(S4C)
N(12)-C(55)-H(55A)
N(12)—C(55)-H(SSB)
H(SSA)-C(55)-H(SSB)
N(12)-C(55)-H(55C)
H(55A)-C(55)-H(55C)
H(SSB)-C(55)-H(55C)
Cl(2)-C(56)-Cl(1)
Cl(2)-C(56)-H(56A)
C1(1)-C(56)-H(56A)
Cl(2)-C(S6)-H(56B)
Cl(1)-C(56)-H(56B)
H(56A)-C(56)-H(56B)

109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5

112.54(15)

109.1
109.1
109.1
109.1
107.8

Table A4.4 Anisotropic displacement parameters (A2 X 103) for

Ti2(dap)3(NNMe2)2(NHNMe2) (37). The anisotropic displacement factor

exponent takes the form: —2 p2 [ h2a"‘2U11 + + 2 h k a* b* U12]

 

 

ull U22 {)3 U23 (113 {112
Ti(l) 15(1) 18(1) 18(1) 0(1) 3(1) 0(1)
Ti(2) 17(1) 16(1) 19(1) 0(1) 2(1) 0(1)
N(l) 22(1) 22(1) 24(1) -1(1) 3(1) 2(1)
N(2) 21(1) 28(1) 22(1) -1(1) 1(1) 2(1)
N(3) 19(1) 22(1) 23(1) -2(1) 4(1) -2(1)
N(4) 25(1) 28(1) 24(1) 2(1) 8(1) -1(1)
N(5) 19(1) 19(1) 17(1) 1(1) 4(1) 0(1)
N(6) 21(1) 20(1) 22(1) 3(1) 6(1) -2(1)
N(7) 20(1) 20(1) 18(1) 1(1) 2(1) 0(1)
N(8) 24(1) 22(1) 19(1) 0(1) -3(1) 1(1)
N(9) 19(1) 21(1) 26(1) -I(1) 2(1) 0(1)
N(10) 21(1) 22(1) 32(1) -3(1) 2(1) -2(1)
N(ll) 23(1) 20(1) 27(1) -4(1) 1(1) -1(1)
N(12) 31(1) 19(1) 32(1) -4(1) 1(1) 1(1)
C(29) 31(1) 33(1) 26(1) -6(1) 4(1) 4(1)
C(30) 37(1) 39(2) 39(1) -14(1) 6(1) 11(1)
C(31) 30(1) 31(1) 47(2) —3(1) 0(1) 12(1)
C(32) 20(1) 22(1) 34(1) 1(1) 2(1) 3(1)
C(33) 24(1) 28(1) 31(1) 4(1) 1(1) 6(1)
C(34) 30(1) 44(2) 25(1) -3(1) -3(1) 5(1)
C(35) 22(1) 37(1) 36(1) 1(1) -4(1) -4(1)
C(36) 18(1) 28(1) 24(1) -2(1) 4(1) 1(1)
C(37) 24(1) 26(1) 26(1) -7(1) 0(1) 2(1)
C(38) 27(1) 20(1) 32(1) -2(1) -2(1) -5(1)
C(39) 20(1) 22(1) 25(1) 0(1) 1(1) -2(1)

245

C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C10)
C1(2)
C(56)

24(1)
43(1)
40(1)
31(1)
35(1)
44(1)
32(1)
24(1)
33(1)
19(1)
19(1)
22(1)
29(1)
28(1)
54(2)
53(2)
35(1)
54(1)
44(2)

25(1)
37(1)
41(2)
33(1)
23(1)
31(1)
26(1)
22(1)
20(1)
36(1)
28(1)
30(1)
42(2)
26(1)
34(1)
22(1)
60(1)
98(1)
74(2)

32(1)
27(1)
41(1)
24(1)
29(1)
20(1)
28(1)
24(1)
30(1)
50(2)
34(1)
51(2)
39(1)
49(2)
39(1)
51(2)
72(1)
46(1)
39(2)

1(1)
11(1)
-70)
0(1)
9(1)
-2(1)
6(1)
-1(1)
-3(1)
-7(1)
-3(1)
-7(1)
-1(1)
0(1)

-16(1)
-2(1)

-200)
8(1)
-5(1)

6(1)
5(1)
24(1)
10(1)
3(1)
-1(1)
4(1)
-1(1)
2(1)
4(1)
3(1)
10(1)
-3(1)
6(1)
10(1)
-8(1)
5(1)
9(1)
-2(1)

-50)
-100)
-6(1)
1(1)
-1(1)
3(1)
7(1)
-2(1)
6(1)
5(1)
0(1)
-3(1)
-5(1)
-7(1)
-5(1)
2(1)
10(1)
14(1)
26(2)

 

246

Table A4.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X

103) for Ti2(dap)3(NNMe2)2(NHNMe2)

 

 

x y z U(eq)
H01) 9212 6 1081 28
H(29) 10912 1 147 541 36
H(30) 12333 -663 596 46
H(31) 12979 -912 1413 43
H(33A) 11161 387 2113 34
H(33B) 12493 645 2157 34
H(34A) 10510 2130 2541 50
H(34B) 1 1 102 3569 2545 50
H(34C) 1 1797 2284 2723 50
H(35A) 13212 2753 2236 48
H(3SB) 12529 4043 2055 48
H(35C) 12911 2931 1716 48
H(36) 9103 4762 2270 28
H(37) 9700 7089 2445 31
H(38) 11173 7711 1906 32
H(40A) 1 1827 6358 1 143 32
H(40B) 12464 5263 1456 32
H(41A) 9868 5463 826 53
H(4IB) 10204 4381 467 53
H(41C) 10878 5765 518 53
H(42A) 12627 4643 632 59
H(4ZB) 1 1956 3268 547 59
H(42C) 12774 3453 986 59
H(43A) 8479 2219 2597 43
H(43B) 7297 1480 2498 43
H(43C) 7552 2849 2249 43

247

H(44A)
EK44B)
1H44cn
H(45A)
EK4SB)
PK45CD
H(46A)
PK46ED
IK46CD
1u47)

IK48)

PK49)

IKSIAQ
£0513)
H(52A)
PKSZB)
ruszcn
1u53A)
ru53rn
H(53C)
H(54A)
PK54B)
1H54c»
H(55A)
PKSSB)
PKSSCD
H(56A)
IK56B)

9159
8095
9241
9053
7902
8974
7409
6942
8128
7859
6053
4495
4616
5330
6332
5828
5047
5220
6280
6459
8077
8209
9249
9314
8233
8213
6046
5495

-518
-641

2639
1807
1246
4528
3816
4573
5094
6298
4550
1736
1479

298
1777

502
-734
-486

-1115

-738

-2309
-1324
-2285
-3166
-2209

7137
5684

1931
2224
2432
105
72
362
774
325
347
1563
1608
1525
1320
1781
609
645
717
1394
1739
1262
240
334
447
1192
1042
1466
714
645

44
44
44
48
48
48
44
44
44
28
33
42
41
41
56
56
56
51
51
51
63
63
63
63
63
63
63
63

 

248

Table A4.6 Torsion angles (°) for T12(dap)3(NNMe2)2(NHNMe2)

 

N(5)-Ti(1)-Ti(2)-N(11)
N(7)-Ti( 1 )-Ti(2)-N(1 1)
N(l)-Ti(1)-Ti(2)-N(1 1)
N(3)-Ti(1)-Ti(2)-N(11)
N(2)-Ti(1 )-Ti(2)-N(l 1 )
N(4)-Ti(1)-Ti(2)-N(1 1)
N(7)-Ti(l)-Ti(2)-N(5)
N(1)-Ti(l )-Ti(2)-N(5)
N(3)-Ti(l)-Ti(2)-N(5)
N(2)-Ti(l)-Ti(2)-N(5)
N(4)-Ti(l)-Ti(2)-N(5)
N(5)-Ti(1)-Ti(2)-N(7)
N(l )-Ti(1)-Ti(2)-N(7)
N(3)-Ti(l)-Ti(2)—N(7)
N(2)-Ti(l)—Ti(2)-N(7)
N(4)-Ti(l)-Ti(2)-N(7)
N(5)-Ti( 1 )-Ti(2)-N(9)
N(7)-Ti(1)-Ti(2)-N(9)
N(l)-Ti(1)-Ti(2)-N(9)
N(3)-Ti(1)-Ti(2)-N(9)
N(2)-Ti(1)-Ti(2)-N(9)
N(4)-Ti(l)-Ti(2)-N(9)
N(5)-Ti(1)-Ti(2)-N(6)
N(7)-Ti(l)-Ti(2)—N(6)
N(1)—Ti(1)-Ti(2)-N(6)
N(3)-Ti(1)-Ti(2)-N(6)
N(2)-Ti(l)-Ti(2)-N(6)
N(4)-Ti(l)—Ti(2)-N(6)
N(5)—Ti(l)-Ti(2)-N(8)

9490(9)
9310(9)
213(7)
-174.85(7)
-74.68(7)
9639(7)
472.0000)
9703(8)
-79.95(9)
2022(9)
-168.71(9)
172.0000)
-90.97(8)
9206(9)
-167.78(9)
329(9)
8856(8)
-83.45(8)
-174.42(7)
861(7)
108.78(7)
-80.15(7)
007(8)
-171.93(8)
9710(6)
-79.88(7)
2029(7)
—168.64(7)
174.56(8)

249

N(7)-Ti(l)-Ti(2)—N(8)

N(1)-Ti(l)-Ti(2)-N(8)

N(3)-Ti(1)-Ti(2)-N(8)

N(2)-Ti(1)-Ti(2)-N(8)

N(4)-Ti(l)-Ti(2)-N(8)

N(5)-Ti(l )-Ti(2)-N(10)
N(7)-Ti(l)-Ti(2)—N(10)
N(1)-Ti(1)-Ti(2)-N(10)
N(3)-Ti(l)-Ti(2)-N(10)
N(2)-Ti(1)-Ti(2)-N(10)
N(4)-Ti(1 )-Ti(2)-N(10)
N(5)-Ti(1)-N(l)-C(29)
N(7)-Ti(1)-N(l)-C(29)
N(3)-Ti(l)—N(1)-C(29)
N(2)-Ti(l)-N(1)—C(29)
N(4)-Ti(1)-N(1)-C(29)
Ti(2)-Ti(l)-N(1)-C(29)
N(5)-Ti(l)-N(l)-C(32)
N(7)-Ti(1)-N(l)-C(32)
N(3)-Ti(l)-N(1)—C(32)
N(2)-Ti(l)-N(1)—C(32)
N(4)-Ti(1)-N(l)-C(32)
Ti(2)-Ti(1)-N(l)-C(32)
N(5)-Ti(l)-N(2)-C(35)
N(7)-Ti(1)-N(2)-C(35)
N(1)-Ti(1)-N(2)-C(35)
N(3)-Ti(1)-N(2)-C(35)
N(4)-Ti(l)—N(2)-C(3S)
Ti(2)-Ti(l)-N(2)-C(35)
N(5)-Ti(l)-N(2)-C(34)
N(7)-Ti(1)-N(2)-C(34)

255(8)
-88.42(6)
9461(7)

-165.22(7)

585(7)

41.7(5)
430.3(5)
138.8(5)
-38.2(5)

62.0(5)
427.0(5)
116.0(2)

24.8(2)
414.1(2)
462.5(2)
-62.2(2)
70.5409)

-66.32(16)
457.5105)
63.5809)
15.1704)
115.490 5)
41 1.7804)
470.2004)

125.9(3)

85.8904)
-67.76(14)
234(14)
175.7102)
-46.43(15)
4 103(3)

250

N(1)-Ti(1)—N(2)-C(34)
N(3)-Ti(1)-N(2)-C(34)
N(4)-Ti(1)-N(2)-C(34)
Ti(2)-Ti(1)-N(2)-C(34)
N(5)-Ti(1 )-N(2)-C(33)
N(7)-Ti(1)-N(2)-C(33)
N(1)-Ti(1)—N(2)-C(33)
N(3)-Ti(l)-N(2)-C(33)
N(4)-Ti(1)-N(2)-C(33)
Ti(2)-Ti(1)-N(2)-C(33)
N(5)-Ti(l)-N(3)—C(36)
N(7)-Ti(l)-N(3)-C(36)
N(1)-Ti(1)—N(3)-C(36)
N(2)-Ti(1)-N(3)-C(36)
N(4)-Ti(1)-N(3)-C(36)
Ti(2)-Ti(1)-N(3)-C(36)
N(5)-Ti(1)-N(3)-C(39)
N(7)-Ti(1)-N(3)-C(39)
N(1)-Ti(1)-N(3)-C(39)
N(2)-Ti(1)-N(3)-C(39)
N(4)-Ti(l)—N(3)-C(39)
Ti(2)-Ti(1)-N(3)-C(39)
N(5)-Ti(1 )-N(4)-C(41)
N(7)-Ti(l)—N(4)-C(41)
N(l)-Ti(1)-N(4)-C(4l)
N(3)-Ti(1 )-N(4)—C(4 1)
N(2)-Ti(1)-N(4)-C(41)
Ti(2)-Ti(1)-N(4)-C(41)
N(5)-Ti(1 )-N(4)-C(42)
N(7)-Ti(1)-N(4)-C(42)
N(1)-Ti(1 )-N(4)-C(42)

251

450.3406)
56.0005)
126.1105)
-60.53(16)
7234(12)

84(4)
31.5702)
174.7802)

115.1202)

58.2503)

3.9509)

89.70(19)

433.9507)
-87.48(18)
170.3209)
40.9709)
174.5905)
-91.76(16)

44.6(2)
91.0606)
41.1305)

440.4904)

-50.5(5)
l9.63(14)
1 1745(14)
91.6304)

469.8203)

1729(16)
472.2(4)
402.0406)
-4.21(l6)

N(3)-Ti(1 )-N(4)—C(42)
N(2)-Ti(l )-N(4)-C(42)
Ti(2)-Ti(l)—N(4)-C(42)
N(5)-Ti(1)-N(4)-C(40)
N(7)-Ti(1)-N(4)-C(40)
N(1)-Ti(l )-N(4)-C(40)
N(3)-Ti(l)-N(4)-C(40)
N(2)-Ti(1)-N(4)-C(40)
Ti(2)-Ti(1)-N(4)-C(40)
N(7)-Ti(l)-N(5)-N(6)
N(l)-Ti(1)-N(5)-N(6)
N(3)-Ti(1)-N(5)-N(6)
N(2)-Ti(l)-N(5)-N(6)
N(4)-Ti(1)-N(5)-N(6)
Ti(2)-Ti(l)-N(5)-N(6)
N(7)-Ti(1)-N(5)-Ti(2)
N(1)-Ti(l)-N(5)-Ti(2)
N(3)-Ti(l)—N(5)—Ti(2)
N(2)-Ti(1 )-N(5)-Ti(2)
N(4)-Ti(1)-N(5)-Ti(2)
N(l 1)-Ti(2)-N(5)-N(6)
N(7)-Ti(2)-N(5)—N(6)
N(9)-Ti(2)-N(5)-N(6)
N(8)-Ti(2)-N(5)-N(6)
N(10)-Ti(2)—N(5)—N(6)
Ti(1)-Ti(2)-N(5)-N(6)
N(l l)-Ti(2)—N(S)-Ti(1)
N(7)-Ti(2)-N(S)-Ti(1)
N(9)-Ti(2)-N(5)-Ti(1)
N(6)-Ti(2)-N(5)-Ti(1)
N(8)-Ti(2)-N(5)-Ti(1)

146.7107)
6852(16)
404.3706)
64.1(5)
134.1703)
428.0003)
22.9202)
55.2703)
131.84(11)
4.702)
93.002)
114.402)
-165.1(12)
74.703)
4.0(11)
5.67(7)
-92.06(7)
115.31(7)
464.16(7)
75.6(5)
-88.51(10)
174.5700)
80.5400)
173.67(9)
5.0104)
179.8903)
91.60(7)
532(7)
9935(7)

479.8903)

-6.22(9)

N(10)-Ti(2)-N(5)-Ti(1)
Ti(1)-N(5)-N(6)-C(43)
Ti(2)-N(5)-N(6)-C(43)
Ti(1)-N(5)-N(6)-C(44)
Ti(2)-N(5)-N(6)-C(44)
Ti(1)-N(5)-N(6)-Ti(2)
N(I l)-Ti(2)—N(6)-N(5)
N(7)-Ti(2)-N(6)-N(5)
N(9)-Ti(2)-N(6)-N(5)
N(8)-Ti(2)-N(6)-N(5)
N(10)—Ti(2)—N(6)-N(5)
Ti(1)-Ti(2)-N(6)-N(5)
N(l 1)-Ti(2)-N(6)-C(43)
N(5)-Ti(2)-N(6)-C(43)
N(7)-Ti(2)-N(6)-C(43)
N(9)-Ti(2)-N(6)-C(43)
N(8)-Ti(2)-N(6)-C(43)
N(10)-Ti(2)-N(6)-C(43)
Ti(1)-Ti(2)-N(6)-C(43)
N(l 1)-Ti(2)-N(6)-C(44)
N(5)-Ti(2)—N(6)-C(44)
N(7)-Ti(2)-N(6)-C(44)
N(9)-Ti(2)-N(6)-C(44)
N(8)-Ti(2)-N(6)-C(44)
N(10)-Ti(2)-N(6)-C(44)
Ti(l)—Ti(2)-N(6)-C(44)
N(5)-Ti(1)-N(7)-N(8)
N(1)-Ti(1)-N(7)-N(8)
N(3)-Ti(1)-N(7)-N(8)
N(2)-Ti(l )-N(7)-N(8)
N(4)-Ti(1 )-N(7)-N(8)

253

474.88(6)
415.001)

415.9505)

117.8(11)
116.8005)
1.0(11)
96.96(10)
-6.27(12)
402.6400)
453(2)
476.4200)
-0.07(9)
462.2205)
100.8208)
94.5406)
4.8205)
85.5(2)
-75.60(15)
100.7505)
-2.91(16)
99.8708)
406.1505)
157.4905)
415.2(2)
83.7005)
99.9505)
37.300)
64.700)
439.4(10)
26.3(12)
150.8(10)

Ti(2)-Ti(l)-N(7)-N(8)
N(5)-Ti(1)-N(7)-Ti(2)
N(1)-Ti(1)-N(7)-Ti(2)
N(3)-Ti(1)-N(7)-Ti(2)
N(2)-Ti(1)-N(7)-Ti(2)
N(4)-Ti(1)-N(7)-Ti(2)
N(l 1 )-Ti(2)-N(7)-N(8)
N(5)-Ti(2)-N(7)-N(8)
N(9)-Ti(2)-N(7)-N(8)
N(6)-Ti(2)—N(7)-N(8)
N(10)-Ti(2)-N(7)-N(8)
Ti(l)-Ti(2)-N(7)-N(8)
N(l 1)-Ti(2)-N(7)-Ti(1)
N(5)-Ti(2)-N(7)-Ti(1)
N(9)-Ti(2)-N(7)-Ti(1)
N(6)-Ti(2)-N(7)-Ti(1)
N(8)-Ti(2)-N(7)-Ti(l)
N(10)-Ti(2)-N(7)—Ti(1)
Ti(l)-N(7)-N(8)-C(45)
Ti(2)-N(7)-N(8)-C(45)
Ti(l)-N(7)-N(8)—C(46)
Ti(2)-N(7)-N(8)-C(46)
Ti(1)-N(7)-N(8)-Ti(2)
N(l 1)-Ti(2)-N(8)-N(7)
N(5)-Ti(2)-N(8)-N(7)
N(9)-Ti(2)-N(8)-N(7)
N(6)-Ti(2)-N(8)-N(7)
N(10)-Ti(2)-N(8)-N(7)
Ti(1)-Ti(2)-N(8)-N(7)
N(l 1)-Ti(2)—N(8)-C(45)
N(5)-Ti(2)-N(8)-C(45)

-31.7(9)
-5.61(7)
9640(7)

407730)
57.9(3)
477.58(7)
82.96(10)
478.7600)
-80.90(10)
474.79(9)
4083(15)
175.9503)
9299(7)
529(7)
103.150)
9.2600)

475.9503)
173.22(7)
-83.7(10)

415.8705)
149.9(9)

1 17.7405)
32.100)
-100.48(10)
1.4302)
100.2900)
12.5(2)
173.1500)
-2.72(9)
-0.47(16)
101.4406)

254

N(7)-Ti(2)-N(8)-C(45)
N(9)-Ti(2)-N(8)-C(45)
N(6)-Ti(2)-N(8)-C(45)
N(10)-Ti(2)-N(8)—C(45)
Ti(1)-Ti(2)-N(8)-C(4S)
N(l 1)-Ti(2)-N(8)-C(46)
N(5)-Ti(2)-N(8)-C(46)
N(7)—Ti(2)-N(8)-C(46)
N(9)-Ti(2)-N(8)—C(46)
N(6)-Ti(2)-N(8)-C(46)
N(10)-Ti(2)-N(8)-C(46)
Ti(l)—Ti(2)-N(8)-C(46)
N(1 1)-Ti(2)-N(9)-C(50)
N(5)-Ti(2)-N(9)-C(50)
N(7)-Ti(2)-N(9)-C(50)
N(6)-Ti(2)-N(9)-C(50)
N(8)-Ti(2)-N(9)-C(50)
N(10)-Ti(2)-N(9)-C(50)
Ti(1)-Ti(2)-N(9)-C(50)
N(l l)-Ti(2)-N(9)-C(47)
N(5)-Ti(2)-N(9)-C(47)
N(7)-Ti(2)-N(9)—C(47)
N(6)-Ti(2)-N(9)-C(47)
N(8)-Ti(2)-N(9)-C(47)
N(10)-Ti(2)-N(9)-C(47)
Ti(1)-Ti(2)-N(9)-C(47)

N(I 1)-Ti(2)—N(10)-C(52)

N(5)-Ti(2)-N(10)—C(52)
N(7)-Ti(2)-N(10)-C(52)
N(9)-Ti(2)-N(10)-C(52)
N(6)-Ti(2)—N(10)—C(52)

255

100.0108)
-159.70(16)
112.5(2)
-86.84(16)
97.2905)
157.3306)
400.7606)
402.1909)
490(16)
-89.7(2)
7096(16)
-104.91(16)
12.8(3)
435.3106)
141.8706)
-97.04(16)
104.0606)
4.0505)
476.9005)
455.1809)
56.7209)
-26.10(19)
94.99(18)
-63.92(18)
469.0209)
15.1209)
-72.76(14)
471.7903)
25.1608)
102.3604)
468.6304)

N(8)-Ti(2)-N(10)-C(52)
Ti(l)-Ti(2)-N(10)-C(52)
N(l 1 )-Ti(2)-N(10)-C(53)
N(5)-Ti(2)-N(10)-C(53)
N(7)-Ti(2)-N(10)—C(53)
N(9)-Ti(2)-N(10)-C(53)
N(6)-Ti(2)-N(10)-C(53)
N(8)-Ti(2)-N(10)-C(53)
Ti(1)-Ti(2)-N(10)-C(53)
N(11)-Ti(2)-N(10)-C(51)
N(5)-Ti(2)-N(10)-C(51)
N(7)-Ti(2)-N(10)-C(51)
N(9)-Ti(2)—N(10)-C(51)
N(6)-Ti(2)-N(10)-C(51)
N(8)-Ti(2)-N(10)-C(51)
Ti(1)-Ti(2)-N(10)-C(51)
N(5)-Ti(2)-N(1 1 )-N(12)
N(7)-Ti(2)-N(1 1)-N(12)
N(9)-Ti(2)-N(1 1)-N(12)
N(6)-Ti(2)-N(1 1)-N(12)
N(8)-Ti(2)-N(1 1 )-N(12)
N(10)-Ti(2)-N(I 1)-N(12)
Ti(l )-Ti(2)-N(1 1)-N(12)
Ti(2)-N0 1)-N(12)-C(55)
Ti(2)-N(l 1)-N(12)-C(54)
C(32)-N(1)-C(29)-C(30)
Ti(1)-N(1)-C(29)-C(30)
N(1)-C(29)-C(30)-C(31)
C(29)-C(30)-C(31)—C(32)
C(30)-C(31)-C(32)-N(1)
C(30)-C(31)-C(32)-C(33)

1826(14)
150.2(4)
47.9105)
51.1207)
145.8304)
-136.97(15)
-47.96(15)
138.9304)
-89.1(5)
169.3305)
70.3007)
92.7507)
45.5504)
73.4605)
99.6505)
32.3(6)
141.2(2)
435.5(2)
-6.8(4)
102.0(2)
974(2)
65(2)
477.3(2)
420.2(2)
119.9(2)
050)
177.4606)
00(3)
0.5(3)
-0.8(3)
175.9(2)

256

C(29)-N(1)-C(32)-C(31)
Ti(1)-N(1 )-C(32)-C(31)
C(29)-N(1)-C(32)-C(33)
Ti(1)-N(1)-C(32)-C(33)
C(35)-N(2)-C(33)-C(32)
C(34)-N(2)-C(33)-C(32)
Ti(l)-N(2)-C(33)-C(32)
C(31)-C(32)-C(33)-N(2)
N(1)-C(32)-C(33)-N(2)

C(39)-N(3)-C(36)-C(37)
Ti(1)-N(3)-C(36)-C(37)
N(3)-C(36)-C(37)-C(38)

C(36)-C(37)—C(38)-C(39)

C(37)-C(38)-C(39)-N(3)

C(37)-C(38)-C(39)-C(40)

C(36)-N(3)-C(39)-C(38)
Ti(1)-N(3)-C(39)-C(38)
C(36)-N(3)-C(39)-C(40)
Ti(l)—N(3)-C(39)-C(40)
C(41)-N(4)-C(40)-C(39)
C(42)-N(4)-C(40)-C(39)
Ti(1)-N(4)-C(40)-C(39)
C(38)-C(39)-C(40)—N(4)
N(3)-C(39)-C(40)-N(4)

C(50)-N(9)-C(47)-C(48)
Ti(2)-N(9)-C(47)-C(48)
N(9)-C(47)—C(48)—C(49)

C(47)-C(48)-C(49)-C(50)

C(48)-C(49)-C(50)-N(9)

C(48)-C(49)-C(50)-C(51)

C(47)-N(9)-C(50)-C(49)

257

0.8(2)

477.4905)
-176.46(18)

5.3(2)
47.90)
164.8707)
42.80(17)
147.5(2)
-36.0(2)
05(2)
179.2504)
01(2)
04(2)
08(2)
475.0(2)
-0.8(2)

-179.66(14)

175.5008)
540)
83.0(2)

-160.95(18)

-30.76(19)
458.8(2)
25.7(3)
-0.6(2)
168.80(14)
04(2)
91(3)
-03(3)
169.3(2)
0.5(2)

Ti(2)-N(9)-C(50)—C(49)
C(47)-N(9)-C(50)-C(51)
Ti(2)-N(9)-C(50)-C(51)
C(49)-C(50)-C(51)—N(10)
N(9)-C(50)-C(51)-N(10)
C(52)-N(10)-C(51)—C(50)
C(53)-N(10)-C(51)-C(50)
Ti(2)-N(10)-C(51)-C(50)

470.1805)
470.9909)

183(3)
159.6(2)
512(3)
875(2)

154.8209)

284(2)

 

258

Table A5.1 Crystal data for 3-mesitylpyrrole (43)

Identification code
Empirical formula

Formula weight
Temperature
Wavelength
Crystal system
Space group

Unit cell dimensions

Volume

Z
Density (calculated)

Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected
Independent reflections
Completeness to theta = 2500"
Absorption correction

Max. and min. transmission

Refinement method

Data / restraints / parameters
Goodness-of-fit on F2

Final R indices [I>23igma(l)]
R indices (all data)

Largest diff. peak and hole

Sb1076

C13 H15 N

185.26

173(2) K

0.71073 A

Orthorhombic

Pbca

a = 10.4998(18)A 01 = 90°
b = 10.8656(17) A [3: 90°
c=17.915(3)A y=90°
2043.9(6) A3

8

1.204 Mg/m3

0.070 mm-1
800

0.37 x 0.34 x 0.23 mm3

2.27 to 27.49°.

-13<=h<=13, -13<=k<=13, —21<=l<=21
20550

2284 [R(int) = 0.0253]

99.4 %

Semi-empirical from equivalents

0.9839 and 0.9750

Full-matrix least-squares on F2

2284/0/130

1.056
R1 = 0.0462, wR2 = 0.1306
R1 = 0.0520, wR2 = 0.1366

0.327 and -0.336 e.A-3

259

Table A5.2 Atomic coordinates (X 104) and equivalent isotropic displacement

parameters (A2 X 103) for 3-mesitylpyrrole. U(eq) is defined as one third of the trace of

the orthogonalized Uij tensor

 

 

x y z U(eq)
N(l) 6987(1) 415(1) 1433(1) 30(1)
C(1) 7831(1) -260(1) 1026(1) 28(1)
C(2) 8902(1) 436(1) 926(1) 25(1)
C(3) 8708(1) 1593(1) 1288(1) 22(1)
C(4) 7508(1) 1539(1) 1598(1) 27(1)
C(5) 9639(1) 2626(1) 1309(1) 21(1)
C(6) 10160(1) 3077(1) 640(1) 23(1)
C(7) 11104(1) 3984(1) 665(1) 26(1)
C(8) 11533(1) 4482(1) 1331(1) 26(1)
C(9) 10970(1) 4069(1) 1992(1) 24(1)
C(10) 10033(1) 3153(1) 1992(1) 21(1)
C(11) 9726(1) 2631(1) -117(1) 33(1)
C(12) 12593(1) 5424(1) 1339(1) 34(1)
C(13) 9481(1) 2744(1) 2728(1) 28(1)

 

260

Table A5.3 Bond lengths (A) and angles (°) for 3-mesitylpyrrole

 

N(1)-C(1) 1.3623(18)
N(1)-C(4) 1.3694(17)
C(1)-C(2) 1.3672(17)
C(2)-C(3) 1.429207)
C(3)-C(4) 1.3775(17)
C(3)-C(5) 1.488506)
C(5)-C(6) 1.406807)
C(5)-C(10) 1.412107)
C(6)-C(7) 1.3990(17)
C(6)-C(1 1) 1.509508)
C(7)-C(8) 1.3852(19)
C(8)-C(9) 1.3973(18)
C(8)-C(12) 1.512108)
C(9)-C(10) 1.3998(17)
C(10)-C(13) 1.508207)
C(1)-N(1)-C(4) 109.60(1 1)
N(1)—C(1)-C(2) 107.87(11)
C(1)-C(2)-C(3) 108.070 1)
C(4)-C(3)-C(2) 105.960 1)
C(4)-C(3)-C(5) 128.490 1)
C(2)-C(3)-C(5) 125.540 1)
N(1)-C(4)-C(3) 108.5002)
C(6)-C(5)-C(10) 1 18.91(11)
C(6)-C(5)-C(3) 1 19.730 1)
C(10)-C(5)-C(3) 121.3500)
C(7)-C(6)-C(5) 1 19.5501)
C(7)-C(6)-C(11) 1 17.950 1)
C(5)-C(6)-C(11) 122.5001)

261

C(8)-C(7)-C(6)
C(7)-C(8)-C(9)
C(7)-C(8)-C(12)
C(9)-C(8)-C(12)
C(8)-C(9)-C(10)
C(9)-C(10)-C(5)
C(9)-C(10)-C(13)
C(5)-C(10)-C(13)

122.2602)
117.8202)
120.8402)
121.3302)
121.7302)
119.6201)
118.6701)
121.7101)

 

Table A5.4 Anisotropic displacement parameters (A2 X 103) for 3-mesitylpyrrole. The
displacement factor exponent takes the form: -2 pi2 [ h2 3*2 U11 + + 2 h k a* b* U12

 

 

1

ull u22 U33 u23 ul3 U12
N(l) 21(1) 29(1) 40(1) 7(1) -1(1) -6(1)
C(1) 30(1) 21(1) 31(1) 3(1) -7(1) -3(1)
C(2) 25(1) 22(1) 28(1) 0(1) _ -2(1) 0(1)
C(3) 21(1) 19(1) 25(1) 3(1) -2(1) 1(1)
C(4) 23(1) 24(1) 36(1) 2(1) 2(1.) 0(1)
C(5) 18(1) 18(1) 26(1) 1(1) 0(1) 2(1)
C(6) 24(1) 19(1) 26(1) -1(1) 2(1) 1(1)
C(7) 27(1) 24(1) 28(1) 3(1) 7(1) -l(1)
C(8) 20(1) 21(1) 37(1) 0(1) 2(1) 0(1)
C(9) 21(1) 23(1) 27(1) -3(1) -3(1) 1(1)
C(10) 18(1) 20(1) 25(1) 1(1) 1(1) 3(1)
C(11) 45(1) 29(1) 24(1) —l(1) 2(1) -6(1)
C(12) 27(1) 32(1) 44(1) -2(1) 4(1) -8(1)
C(13) 26(1) 33(1) 24(1) 2(1) 0(1) -2(1)

 

263

Table A5.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X

103) for 3-mesitylpyrrole

 

 

X y 2 U(CQ)
H0) 6224 168 1570 36
H(IA) 7699 4071 844 33
H(2) 9645 194 661 30
H(4) 7110 2173 1878 33
H0) 1 1463 4268 210 32
H(9) 1 1230 4420 2453 29
H0 1A) 9862 3281 488 49
H0 13) 8819 2423 97 49
H(11C) 10217 1900 -258 49
H02A) 13404 5013 1445 52
H023) 12422 6039 1727 52
H(12C) 12641 5830 852 52
H(13A) 9964 3119 3138 42
H033) 9532 1846 2767 42
H(13C) 8588 3002 2760 42

 

Table A5.6 Torsion angles (°) for 3-mesitylpyrrole

 

C(4)-N(1)-C(1)-C(2)
N(l)-C(l)-C(2)-C(3)
C(1)-C(2)-C(3)-C(4)
C(1)-C(2)-C(3)-C(5)
C(1)-N(1)-C(4)-C(3)
C(2)-C(3)-C(4)-N(1)
C(5)-C(3)-C(4)-1\l(1 )
C(4)-C(3)-C(5)-C(6)
C(2)-C(3)-C(5)-C(6)
C(4)-C(3)-C(5)-C(10)
C(2)-C(3)-C(5)—C(10)
C(10)-C(5)-C(6)-C(7)
C(3)-C(5)-C(6)-C(7)
C(10)-C(5)—C(6)-C(1 1)
C(3)-C(5)-C(6)-C(1 1)
C(5)-C(6)-C(7)-C(8)
C(1 1)-C(6)—C(7)-C(8)
C(6)-C(7)—C(8)-C(9)
C(6)-C(7)-C(8)-C(12)
C(7)-C(8)-C(9)-C(10)
C(12)-C(8)—C(9)-C(10)
C(8)-C(9)-C(lO)-C(5)
C(8)-C(9)—C(10)—C(13)
C(6)-C(5)-C(10)-C(9)
C(3)-C(5)-C(lO)-C(9)
C(6)-C(5)-C(10)-C(13)
C(3)-C(5)-C(10)-C(l3)

-02105)
0.0405)
0.1404)
479.5601)
031(15)
-02704)
179.4201)
426.6104)
53.0207)
54.6708)
425.7003)
3.5107)
475.2401)
-175.6l(11)
5.6408)
4.4309)
177.7302)
4.4109)
1774702)
2.1708)
4767002)
-0.08(18)
179.2701)
-2.78(17)
175.9600)
177.8901)
-3.38(17)

 

265

Table .46.] Crystal data for T1(dap3 ’mes)2(NMe2)2 (45)

Identification code
Empirical formula

F orrnula weight
Temperature
Wavelength
Crystal system
Space group

Unit cell dimensions

Volume

Z
Density (calculated)

Absorption coefficient

F(000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected
Independent reflections
Completeness to theta = 25.00°
Absorption correction

Max. and min. transmission
Refinement method

Data / restraints / parameters
Goodness-of-fit on F2

Final R indices [I>2sigma(l)]
R indices (all data)

sbfinal
C365 H55 Cl N6 Ti

661.22

173(2) K

0.71073 A

Monoclinic

P 21/n

a=12.8140(4)A 01=90°

b = 18.4577(7) A [3 = 105.887(2)o
c = l6.0983(6) A y = 90°
3662.1(2) A3

4

1.199 Mg/m3

0.340 mm—1
1420

0.41 x 0.23 x 0.22 mm3

2.1210 25.38°.

-15<=h<=15, —22<=k<=22, —19<=1<=19
46233

6730 [R(int) = 0.0301]

100.0 %

Semi-empirical from equivalents
0.9290 and 0.8719

Full-matrix least-squares on F2

6730 / 0 / 420

1.032
R1 = 0.0393, wR2 = 0.1005
R1 = 0.0473, wR2 = 0.1063

266

Largest diff. peak and hole 0.686 and —0.746 e.A"3

Table A6.2 Atomic coordinates (X 104) and equivalent isotropic displacement
parameters (A2 X 103) for Ti(dap3_mes)2(NMe2)2. U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor

 

 

X y Z U(CQ)
Ti(l) 2071(1) 104560) 3218(1) 22(1)
N(l) 3101(1) 9706(1) 2923(1) 24(1)
N(2) 1799(1) 104620) 1588(1) 28(1)
N(3) 784(1) 9707(1) 2941(1) 26(1)
N(4) 476(1) 110790) 3392(1) 29(1)
N(5) 2497(1) 102220) 4418(1) 26(1)
N(6) 2776(1) 113740) 3244(1) 29(1)
C(1) 3915(1) 9307(1) 3463(1) 25(1)
C(2) 4307(1) 8788(1) 3015(1) 24(1)
C(3) 3702(1) 8877(1) 2134(1) 26(1)
C(4) 2978(1) 9429(1) 2108(1) 25(1)
C(5) 2061(2) 9711(1) 1392(1) 28(1)
C(6) 2607(2) 109500) 1384(1) 39(1)
C(7) 719(2) 106460) 1021(1) 43(1)
C(8) 5153(1) 8245(1) 3401(1) 24(1)
C(9) 5041(1) 7802(1) 4085(1) 26(1)
C(10) 5872(2) 7322(1) 4477(1) 29(1)
C(1 1) 6810(2) 7256(1) 4209(1) 29(1)
C(12) 6901(2) 7685(1) 3523(1) 28(1)
C(13) 6096(1) 8170(1) 3114(1) 25(1)
C(14) 6256(2) 8612(1) 2373(1) 34(1)
C(15) 4036(2) 7820(1) 4401(1) 33(1)
C(16) 7685(2) 6724(1) 4631(1) 43(1)
C(17) 703(2) 8988(1) 2682(1) 27(1)
C(18) 442(2) 8651(1) 2894(1) 28(1)

C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)

C1(1S)
C0S)

-615(2)
-29(2)
-28(2)

529(2)
703(2)

492(1)

4225(2)
4577(2)
4215(2)

479(2)
4 13(2)

4620(2)
4568(2)

692(2)
3966(2)
2491(2)
23 18(2)
3067(2)
1075(1)

276(5)

9183(1)
9806(1)

105060)
113090)
117040)

7884(1)
7687(1)
6970(1)
6441(1)
6643(1)
7352(1)
8243(1)
5661(1)
7539(1)

113320)
121110)

9507(1)

106800)

5300(1)
4747(3)

3318(1)
3337(1)
3799(1)
2591(1)
3992(2)
2725(1)
1935(1)
1801(1)
2425(1)
3198(1)
3359(1)
1234(1)
2270(2)
4210(1)
3588(1)
2953(2)
4744(1)
5142(1)
5394(1)
4637(4)

33(1)
28(1)
31(1)
41(1)
42(1)
28(1)
29(1)
33(1)
34(1)
32(1)
30(1)
38(1)
49(1)
42(1)
38(1)
41(1)
34(1)
37(1)
91(1)
62(2)

 

268

Table A6.3 Bond lengths (A) and angles (°) for Ti(dap3—mes)2(NMe2)2

 

Ti(1)-N(5)
Ti(l)—N(6)
Ti(1)-N(1)
Ti(1)-N(3)
Ti(l)-N(4)
Ti(1)-N(2)
N(1)-C(1)
N(1)-C(4)
N(2)-C(7)
N(2)-C(6)
N(2)-C(5)
N(3)-C(20)
N(3)-C(17)
N(4)-C(22)
N(4)-C(21)
N(4)-C(23)
N(5)-C(35)
N(5)-C(36)
N(6)-C(34)
N(6)-C(33)
(3(1)-C(2)
C(1 )-H( 1)
C(2)-C(3)
C(2)-C(8)
C(3)-C(4)
C(3)-H(3)
C(4)-C(5)

C(5)-H(5A)

C(5)-H(5B)

1.9076(15)
1.9156(16)
2.054805)
2.103505)
2.427605)
2.551006)
1.375(2)
1.377(2)
1.474(3)
1.477(3)
1.480(2)
1.375(2)
1.387(2)
1.476(3)
1.483(2)
1.483(3)
1.462(2)
1.463(2)
1.454(3)
1.474(3)
1.375(2)
0.9500
1.428(2)
1.482(2)
1.371(3)
0.9500
1.496(3)
0.9900
0.9900

C(6)-H(6A)
C(6)-H(6B)
C(6)-H(6C)
C(7)-H(7A)
C(7)-H(7B)
C(7)-H(7C)
C(8)-C(9)
C(8)-C(13)
C(9)-C(10)
C(9)-C(15)
C(10)-C(1 1)
C(10)-H(10)
C(1 1)-C(12)
C(1 1)-C(16)
C(12)-C(13)
C(12)-H(12)
C(13)-C(14)
C(14)-H(14A)
C(14)-H(14B)
C(14)-H(14C)
C(15)—H(15A)
C(15)-H(lSB)
C(15)-H(15C)
C(16)-H(16A)
C(16)—H(16B)
C(16)-H(16C)
C(17)-C(18)
C(17)-H(17)
C(18)-C(19)
C(18)-C(24)
C(19)—C(20)

0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.41 1(3)
1.414(2)
1.396(3)
1.508(3)
1.388(3)
0.9500
1.390(3)
1.506(3)
1.388(3)
0.9500
1.505(3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.370(3)
0.9500
1.422(3)
1.489(3)
1.370(3)

270

C(19)-H(19)
C(20)-C(21)
C(21)-H(21A)
C(21)-H(213)
C(22)-H(22A)
C(22)-H(22B)
C(22)-H(22C)
C(23)-H(23A)
C(23)-H(23B)
C(23)-H(23C)
C(24)-C(29)
C(24)-C(25)
C(25)-C(26)
C(25)-C(30)
C(26)-C(27)
C(26)-H(26)
C(27)-C(28)
C(27)-C(31)
C(28)-C(29)
C(28)-H(28)
C(29)-C(32)
C(30)-H(30A)
C(30)-H(3OB)
C(30)-H(30C)
C(31)-H(31A)
C(31)-H(3IB)
C(31)-H(31C)
C(32)-H(32A)
C(32)-H(3ZB)
C(32)-H(32C)
C(33)-H(33A)

0.9500
1.490(3)
0.9900
0.9900
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.402(3)
1.406(3)
1.396(3)
1.507(3)
1.385(3)
0.9500
1.391(3)
1.509(3)
1.391(3)
0.9500
1.512(3)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800

C(33)-H(33B)
C(33)-H(33C)
C(34)-H(34A)
C(34)-H(34B)
C(34)-H(34C)
C(35)-H(35A)
C(35)-H(353)
C(35)-H(35C)
C(36)-H(36A)
C(36)-H(36B)
C(36)-H(36C)
Cl(lS)-C(IS)
C1(IS)-C(1S)#1
C(IS)-Cl(1S)#1
C(IS)-C(IS)#1
C(IS)-H(1SA)
C(1S)-H0SB)

N(5)-Ti(1)-N(6)
N(5)-Ti(1)-N(1)
N(6)-Ti(1)-N(1)
N(5)-Ti(1)-N(3)
N(6)-Ti(1)-N(3)
N(1)-Ti(1)-N(3)
N(5)-Ti(l)—N(4)
N(6)-Ti(l)-N(4)
N(1)—Ti(1)-N(4)
N(3)-Ti(l)-N(4)
N(5)-Ti(l)-N(2)
N(6)-Ti(l)-N(2)
N(1)-Ti(1)-N(2)

0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.701(6)
1.721(6)
1 .721(6)
1.78700)

0.9601
0.9600

100.08(7)
9333(6)
105.75(6)
9326(6)
15745(7)
91 .41(6)
9041(6)
8915(6)
163.71(6)
7254(6)
164.48(6)
87.] 1(6)
7139(5)

N(3)-Ti(1)-N(2)
N(4)-Ti(l )-N(2)
C(1)-N(1)-C(4)
C(1)-N(1)—Ti(l)
C(4)-N(1)-Ti(1)
C(7)-N(2)-C(6)
C(7)-N(2)-C(5)
C(6)-N(2)-C(5)
C(7)-N(2)-Ti(1)
C(6)-N(2)-Ti(l)
C(5)-N(2)-Ti(1)
C(20)-N(3)-C(17)
C(20)-N(3)-Ti(1)
C(17)-N(3)-Ti(l)
C(22)-N(4)-C(21)
C(22)-N(4)-C(23)
C(21)-N(4)-C(23)
C(22)-N(4)-Ti(1)
C(21)-N(4)-Ti(l)
C(23)-N(4)-Ti(l)
C(35)-N(5)-C(36)
C(35)-N(5)-Ti(1)
C(36)-N(5)-Ti(1)
C(34)-N(6)-C(33)
C(34)-N(6)-Ti(1)
C(33)-N(6)-Ti(l)
N(1)-C(1)-C(2)
N(1)-C(1)-H(l)
C(2)-C( 1 )-H( 1)
C(1)-C(2)-C(3)
C(1)-C(2)-C(8)

8461(6)
103.53(5)
105.8404)
129.7002)
123.8402)
108.5706)
108.2505)
108.0605)
1 1863(12)
108.93(11)
103.9200)
105.2605)
117.6302)
133.0602)
107.87(16)
108.09(16)
107.3605)
1 1647(12)
101.2601)
115.0202)
109.2305)
122.5302)
128.2103)
108.25(l6)
138.2604)
113.2303)
111.3905)
124.3
124.3
105.3206)
125.5606)

273

C(3)-C(2)-C(8)
C(4)-C(3)-C(2)
C(4)-C(3)—H(3)
C(2)-C(3)-H(3)
C(3)-C(4)-N(1)
C(3)-C(4)-C(5)
N(1)-C(4)-C(5)
N(2)-C(5)-C(4)
N(2)-C(5)-H(5A)
C(4)-C(5)-H(5A)
N(2)-C(5)-H(5B)
C(4)-C(5)-H(5B)
H(5A)-C(5)-H(SB)
N(2)-C(6)-H(6A)
N(2)-C(6)—H(6B)
H(6A)-C(6)-H(6B)
N(2)-C(6)-H(6C)
H(6A)-C(6)-H(6C)
H(6B)-C(6)-H(6C)
N(2)-C(7)-H(7A)
N(2)-C(7)-H(7B)
H(7A)-C(7)-H(7B)
N(2)-C(7)-H(7C)
H(7A)-C(7)-H(7C)
H(7B)-C(7)-H(7C)
C(9)-C(8)-C(13)
C(9)-C(8)-C(2)
C(13)-C(8)-C(2)
C(10)—C(9)-C(8)
C(10)-C(9)-C(15)
C(8)-C(9)-C(15)

129.0906)
107.1505)
126.4
126.4
110.2906)
131.5806)
117.8305)
109.6905)
109.7
109.7
109.7
109.7
108.2
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
118.5006)
119.9906)
121.49(16)
1 1950(16)
118.5307)
121.9707)

C(1 1)-C(10)-C(9)
C(1 1)-C(10)-H(10)
C(9)-C(10)-H(10)
C(10)-C(1 1)-C(12)
C(10)-C(1 1)-C(16)
C(12)-C(1 1)-C(l6)
C(13)-C(12)-C(11)
C(13)-C(12)-H(12)
C(11)-C(12)-H(12)
C(12)-C(13)—C(8)
C(12)-C(13)-C(14)
C(8)-C(13)-C(14)
C(13)-C(14)-H(14A)
C(13)-C(14)-H(14B)
H(14A)-C(14)-H(14B)
C(13)-C(14)-H(14C)
H(14A)-C(14)-H(14C)
H(14B)-C(14)-H(14C)
C(9)-C(15)—H(15A)
C(9)-C(15)-H(15B)
H(15A)-C(15)-H(ISB)
C(9)-C(15)-H(15C)
H(15A)-C(15)-H(15C)
H(153)-C(15)-H05C)
C(1 1)-C(16)-H(16A)
C(1 1)-C(16)-H(168)
H(16A)-C(16)-H(16B)
C(1 1)-C(16)-H(16C)
H(l6A)-C(16)-H(16C)
H(16B)-C(16)-H(16C)
C(18)-C(17)-N(3)

122.250 7)
118.9
118.9
117.710 7)
121.2708)
121.0008)
122.0707)
119.0
119.0
1 1993(17)
118.76(16)
121.30(16)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
110.980 6)

C(18)—C(17)-H(17)
N(3)-C(17)-H(17)
C(17)-C(18)-C(19)
C(17)-C(18)-C(24)
C(19)-C(18)-C(24)
C(20)-C(19)-C(18)
C(20)-C(19)-H(19)
C(18)-C(19)-H(19)
C(19)-C(20)-N(3)
C(19)-C(20)-C(21)
N(3)-C(20)-C(21)
N(4)-C(21)-C(20)
N(4)-C(21)-H(21A)
C(20)-C(21)-H(21A)
N(4)-C(21)—H(ZlB)
C(20)-C(21)-H(213)
H(21A)-C(21)-H(213)
N(4)-C(22)-H(22A)
N(4)-C(22)-H(ZZB)
H(22A)-C(22)-H(ZZB)
N(4)-C(22)-H(22C)
H(22A)—C(22)—H(22C)
H(223)-C(22)-H(22C)
N(4)-C(23)—H(23A)
N(4)-C(23)—H(23B)
H(23A)-C(23)—H(23B)
N(4)-C(23)-H(23C)
H(23A)-C(23)-H(23C)
H(23B)-C(23)-H(23C)
C(29)-C(24)-C(25)
C(29)-C(24)—C(18)

124.5
124.5
106.0807)
127.2007)
126.7106)
106.6906)
126.7
126.7
110.97(l6)
131.6407)
1 1676(16)
109.7405)
109.7
109.7
109.7
109.7
108.2
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
119.330 7)
120.420 7)

276

C(25)-C(24)-C(18)
C(26)-C(25)-C(24)
C(26)-C(25)-C(30)
C(24)-C(25)-C(30)
C(27)-C(26)-C(25)
C(27)-C(26)-H(26)
C(25)-C(26)-H(26)
C(26)-C(27)-C(28)
C(26)-C(27)-C(31)
C(28)-C(27)-C(31)
C(27)-C(28)—C(29)
C(27)-C(28)-H(28)
C(29)-C(28)-H(28)
C(28)-C(29)-C(24)
C(28)-C(29)—C(32)
C(24)-C(29)-C(32)
C(25)-C(30)—H(30A)
C(25)-C(30)-H(30B)
H(30A)-C(30)-H(3OB)
C(25)-C(30)-H(30C)
H(30A)-C(30)-H(30C)
H(3OB)-C(30)-H(30C)
C(27)-C(31)—H(3 1A)
C(27)-C(31)-H(3 13)
H(31A)-C(31)-H(3IB)
C(27)-C(31)—H(31C)
H(31A)-C(31)-H(31C)
H(3lB)-C(31)-H(31C)
C(29)-C(32)-H(32A)
C(29)-C(32)-H(323)
H(32A)-C(32)-H(3ZB)

120.2307)
119.45(18)
120.1408)
120.4008)
121.7708)
119.1
119.1
118.02(18)
121.7909)
120.1609)
122.0309)
119.0
119.0
119.3908)
119.7108)
120.9008)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5

277

C(29)-C(32)-H(32C)
H(32A)-C(32)-H(32C)
H(323)-C(32)-H(32C)
N(6)-C(33)-H(33A)
N(6)-C(33)-H(33B)
H(33A)-C(33)-H(33B)
N(6)-C(33)-H(33C)
H(33A)—C(33)-H(33C)
H(33B)-C(33)-H(33C)
N(6)-C(34)-H(34A)
N(6)-C(34)-H(34B)
H(34A)—C(34)-H(34B)
N(6)-C(34)-H(34C)
H(34A)—C(34)-H(34C)
H(34B)-C(34)-H(34C)
N(5)-C(3S)-H(35A)
N(5)-C(35)-H(353)
H(35A)-C(35)-H(35B)
N(5)-C(35)-H(35C)
H(35A)-C(35)-H(35C)
H(3SB)-C(35)-H(35C)
N(5)-C(36)—H(36A)
N(5)-C(36)-H(36B)
H(36A)-C(36)-H(36B)
N(5)-C(36)-H(36C)
H(36A)-C(36)-H(36C)
H(36B)-C(36)-H(36C)
C(IS)-C1(1S)-C(1S)#l
C1(IS)-C(1S)-CI(IS)#1
C1(IS)-C(IS)-C(IS)#1

109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
629(3)
117.1(3)
591(3)

C1(IS)#l—C(lS)-C(IS)#I 58.0(3)

278

Cl(lS)-C(1S)-H(1SA) 108.0
C1(IS)#1-C(1S)-H(ISA) 108.0
C(1S)#1-C(lS)-H(ISA) 126.4
C1(IS)-C(1S)-H(1SB) 108.0
Cl(1S)#1-C(1S)-H(ISB) 108.0
C(1S)#1-C(IS)-H(ISB) 126.4
H(ISA)-C(1S)-H(1SB) 107.3

 

Table A6.4 Anisotropic displacement parameters (A2 X 103) for Ti(dap3-mes)2(NMe2)2.

The anisotropic displacement factor exponent takes the form: —2 pi2 [ h2 a"‘2 U11 + +
2 h k a* 15* 1112 ]

 

 

ull u22 u33 U23 ul3 1112
Ti(l) 22(1) 22(1) 23(1) -2(1) 7(1) 0(1)
N(l) 24(1) 26(1) 22(1) -3(1) 6(1) 1(1)
N(2) 31(1) 26(1) 27(1) 1(1) 7(1) 4(1)
N(3) 25(1) 27(1) 28(1) -2(1) 9(1) -1(1)
N(4) 31(1) 25(1) 33(1) -2(1) 11(1) 3(1)
N(5) 27(1) 28(1) 25(1) -3(1) 8(1) 0(1)
N(6) 31(1). 26(1) 31(1) -3(1) 11(1) -1(1)
C(1) 23(1) 29(1) 22(1) —1(1) 5(1) 1(1)
C(2) 24(1) 24(1) 25(1) -2(1) 8(1) -2(1)
C(3) 29(1) 26(1) 24(1) —3(1) 9(1) 1(1)
C(4) 27(1) 25(1) 23(1) -2(1) 8(1) -l(1)
C(5) 32(1) 29(1) 23(1) -2(1) 6(1) 2(1)
C(6) 55(1) 32(1) 34(1) 2(1) 20(1) -5(1)
C(7) 42(1) 48(1) 34(1) 2(1) 3(1) 17(1)
C(8) 25(1) 23(1) 24(1) -5(1) 5(1) -1(1)
C(9) 28(1) 26(1) 24(1) -4(1) 7(1) -2(1)

279

C(10)
C(1 1)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)

C1(1S)

C(lS)

37(1)
30(1)
25(1)
27(1)
33(1)
35(1)
45(1)
27(1)
26(1)
28(1)
24(1)
29(1)
38(1)
48(1)
25(1)
27(1)
31(1)
34(1)
32(1)
26(1)
42(1)
61(2)
42(1)
32(1)
50(1)
39(1)
40(1)
102(1)
86(4)

26(1)
26(1)
28(1)
23(1)
35(1)
35(1)
42(1)
28(1)
31(1)
37(1)
31(1)
32(1)
40(1)
30(1)
30(1)
33(1)
36(1)
31(1)
33(1)
35(1)
40(1)
33(1)
46(1)
39(1)
28(1)
35(1)
41(1)
106(1)
51(3)

24(1)
28(1)
31(1)
26(1)
39(1)
33(1)
39(1)
27(1)
27(1)
38(1)
30(1)
35(1)
44(1)
52(1)
32(1)
30(1)
32(1)
41(1)
34(1)
30(1)
31(1)
51(1)
34(1)
44(1)
49(1)
28(1)
27(1)
72(1)
57(3)

1(1)
-4(1)
-5(1)
-4(1)
7(1)
3(1)
6(1)
-4(1)
-1(1)
-2(1)
-2(1)
-1(1)
3(1)
40(1)
-3(1)
-2(1)
-70)
-5(1)
4(1)
-2(1)
0(1)
5(1)
0(1)
9(1)
-2(1)
4(1)
-3(1)
-8(1)
8(3)

7(1)
3(1)
8(1)
7(1)
17(1)
14(1)
7(1)
9(1)
7(1)
15(1)
10(1)
14(1)
10(1)
24(1)
13(1)
12(1)
8(1)
16(1)
14(1)
10(1)
9(1)
12(1)
2(1)
13(1)
18(1)
10(1)
5(1)
35(1)
35(3)

4(1)
2(1)
2(1)
-2(1)
4(1)
-1(1)
13(1)
-1(1)
5(1)
-20)
1(1)
3(1)
11(1)
2(1)
-3(1)
0(1)
-30)
-3(1)
1(1)
4(1)
0(1)
40(1)
-2(1)
-9(1)
-4(1)
1(1)
-3(1)
-240)
25(3)

 

Table A6.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X
103) for T1(dap3 'mes)2(NMe2)2

 

 

x y z U(eq)
H(l) 4174 9381 4069 30
H(3) 3785 8604 1656 31
H(5A) 2268 9702 842 34
H(53) 1416 9398 1324 34
H(6A) 2586 10898 774 58
H(6B) 3333 10825 1746 58
H(6C) 2439 11453 1498 58
H(7A) 547 1 1 150 1 120 65
H(7B) 173 10325 1 150 65
H(7C) 719 10584 416 65
H00) 5794 7031 4943 35
H02) 7534 7645 3327 33
H(14A) 7034 8673 2437 51
H043) 5918 9089 2371 51
H(14C) 5919 8363 1828 51
H(15A) 3953 7354 4667 50
H053) 3399 7910 3912 50
H(15C) 4103 8208 4828 50
H(16A) 7573 6559 5178 64
H063) 8396 6959 4741 64
H(16C) 7658 6308 4248 64
H07) 1171 8759 2395 32
H09) 4219 9118 3545 40
H(21A) -782 10645 3776 37
H(213) 384 10451 4413 37
H(22A) 559 10889 2213 61
H(223) 4 1 1672 2294 61

281

1K22C)
r0234)
r8233)
FK23C)
1K26)

1H28)

1H3OA)
PK30B)
1K30C)
1K3LA)
PK31B)
1H31C)
1K32A)
1K32B)
IK32C)
IK33A)
10333)
1K33C)
IK34A)
1u343)
1K34C)
1K35A)
13353)
1K35C)
1K36A)
IK368)
IK36C)
IKISA)
1H1SB)

-961
963
1259
37
-2077
-219
-1024
~1875
-2218
-957
-2167
-1808
761
436
1400
4306
4172
4209
2629
1721
2932
3008
2022
1803
2648
3151
3784
573
324

11520
12113
11569
11844
6841
6285
8378
8674
8039
5367
5626
5482
7129
7966
7644
11441
10842
11683
12435
12132
12263
9313
9180
9547
10704
11169
10474
4267
4903

2735
3715
4520
4138
1269
3630

991
1476

777
2207
1741
2760
4608
4459
4114
3127
3809
4058
3453
2635
2573
5100
4257
5093
5567
4931
5413
4728
4080

61
62
62
62
40
39
57
57
57
73
73
73
63
63
63
57
57
57
62
62
62
51
51
51
55
55
55
74
74

 

1‘0
00
1Q

Table A6.6 Torsion angles (°) for Ti(dap3-mes)2(NMe2)2

 

N(5)-Ti(1)-N(1)-C(1)
N(6)-Ti(l)—N(1)-C(l)
N(3)-Ti(1)-N(1)-C(1)
N(4)-Ti(1)-N(1)-C(1)
N(2)-Ti(1 )-N(1 )-C( 1)
N(5)-Ti(1)-N(1)-C(4)
N(6)-Ti(l)-N(1)-C(4)
N(3)-Ti(1)-N(l)-C(4)
N(4)-Ti(1)-N(1)-C(4)
N(2)-Ti(1)-N(1)-C(4)
N(5)-Ti(l)-N(2)-C(7)
N(6)-Ti(1)-N(2)-C(7)
N(1)-Ti(1)-N(2)-C(7)
N(3)-Ti(1)-N(2)-C(7)
N(4)-Ti(1)-N(2)-C(7)
N(5)-Ti(1)-N(2)-C(6)
N(6)-Ti(1)-N(2)-C(6)
N(1)-Ti(1)-N(2)-C(6)
N(3)-Ti(1)-N(2)-C(6)
N(4)-Ti(1)-N(2)-C(6)
N(5)-Ti(1)-N(2)-C(5)
N(6)-Ti(1)-N(2)-C(5)
N(1)-Ti(1)-N(2)-C(5)
N(3)-Ti(1)-N(2)-C(5)
N(4)-Ti(1 )-N(2)-C(5)
N(5)-Ti(1)-N(3)-C(20)
N(6)-Ti(1)-N(3)-C(20)
N(1)-Ti(1)-N(3)-C(20)
N(4)-Ti(l)-N(3)-C(20)

-10.30(l6)
91.1606)
403.6506)
413.3(2)
172.5107)
159.2804)
99.2604)
65.93(14)
563(3)
47.9103)
139.2(2)
402.6005)
149.71(16)
5640(15)
44.1705)
960(2)
22.2103)
85.4803)
-l78.79(13)
110.64(12)
19.0(3)
137.2102)
29.5301)
53.7901)
4 34.360 1)
61.4804)
550(2)
1549004)
-279203)

283

N(2)-Ti(l)-N(3)-C(20)
N(5)-Ti(1)-N(3)-C(17)
N(6)-Ti(1)-N(3)-C(17)
N(l)-Ti(1)-N(3)-C(17)
N(4)-Ti(l)-N(3)-C(17)
N(2)-Ti(1)-N(3)-C(17)
N(5)-Ti(1)-N(4)-C(22)
N(6)-Ti(1)-N(4)-C(22)
N(1)-Ti(l)-N(4)-C(22)
N(3)-Ti(l)-N(4)-C(22)
N(2)-Ti(l)—N(4)-C(22)
N(5)-Ti(l)-N(4)-C(21)
N(6)-Ti(l)-N(4)-C(21)
N(l)-Ti(l)-N(4)-C(21)
N(3)-Ti(1)-N(4)-C(21)
N(2)-Ti(l)-N(4)-C(21)
N(5)-Ti(l)-N(4)-C(23)
N(6)-Ti(1)-N(4)-C(23)
N(1)-Ti(1)-N(4)-C(23)
N(3)-Ti(l)-N(4)—C(23)
N(2)-Ti(1)-N(4)-C(23)
N(6)-Ti(l)-N(5)-C(3S)
N(1)-Ti(1)-N(5)-C(35)
N(3)-Ti(1)-N(5)-C(35)
N(4)-Ti(l)—N(5)-C(35)
N(2)-Ti(1)-N(5)-C(35)
N(6)-Ti(1)-N(5)-C(36)
N(1)-Ti(1)-N(5)-C(36)
N(3)-Ti(l)-N(5)-C(36)
N(4)-Ti(1)-N(5)-C(36)
N(2)-Ti(1)-N(5)-C(36)

4339404)
92.1207)
141.4108)

1.3007)
178.48(18)
72.4606)

470.9704)

8895(14)
57.6(3)
-77.68(14)
2.1305)
5430(12)
454.3802)
491(3)
38.99(11)
118.8001)
61.0704)
-39.0l(14)
164.4709)
154.3605)

425.8303)

-l69.64(14)
52.9904)
2861(15)
101.1504)

53.0(3)
7.8007)
114.4506)

453.9506)

81.4106)
124.5(2)

284

N(5)-Ti(1)-N(6)-C(34)
N(1)-Ti(1)-N(6)—C(34)
N(3)-Ti(1)-N(6)-C(34)
N(4)-Ti(1)-N(6)-C(34)
N(2)-Ti(1)-N(6)-C(34)
N(5)-Ti(1)-N(6)-C(33)
N(1)-Ti(1)-N(6)-C(33)
N(3)-Ti(1)-N(6)-C(33)
N(4)-Ti(1)-N(6)-C(33)
N(2)-Ti(1)-N(6)-C(33)
C(4)-N(1)-C(1)-C(2)
Ti(1)-N(1)-C(1)-C(2)
N(1)—C(1)-C(2)-C(3)
N(1)-C(1)-C(2)-C(8)
C(1)—C(2)-C(3)—C(4)
C(3)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-1\l(1 )
C(2)-C(3)-C(4)-C(5)
C(1)-N(1)-C(4)-C(3)
Ti(1)-N(1)-C(4)-C(3)
C(1)-N(1)-C(4)-C(5)
Ti(l)—N(1)-C(4)-C(5)
C(7)-N(2)-C(5)-C(4)
C(6)-N(2)-C(5)-C(4)
Ti(l)-N(2)-C(5)-C(4)
C(3)-C(4)-C(5)-N(2)
N(1)-C(4)-C(5)-N(2)
C(1)-C(2)-C(3)-C(9)
C(3)-C(2)-C(8)-C(9)
C(1)-C(2)—C(8)-C(13)
C(3)-C(2)-C(8)-C(13)

426.0(2)
137.6309)
06(3)
5570)
679(2)
60.8204)
-35.59(14)
473.8205)
151.0803)
405.3303)
010)
170.9202)
07(2)
477.3506)
4.0(2)
176.9207)
1.0(2)
472.4209)
-0.6(2)
472.2802)
173.8706)
2.2(2)
463.6306)
78.96(18)
-36.66(16)
458.9309)
280(2)
529(3)
424.7(2)
425.7(2)
567(3)

C(13)-C(8)-C(9)-C(10)
C(2)-C(8)-C(9)—C(10)
C(13)-C(8)-C(9)-C(15)
C(2)-C(8)-C(9)-C(15)
C(8)-C(9)-C(10)-C(1 1)
C(15)-C(9)-C(10)-C(1 1)
C(9)-C(10)-C(1 1)-C(12)
C(9)-C(10)-C(1 1)-C(16)
C(10)-C(1 1)-C(12)-C(1 3)
C(16)-C(l 1)-C(12)-C(13)
C(1 1)-C(12)-C(13)—C(8)
C(1 1)-C(12)-C(13 )-C(14)
C(9)-C(8)-C(13)-C(12)
C(2)-C(8)-C(13)-C(12)
C(9)-C(8)—C(13)-C(14)
C(2)-C(8)-C(13)-C(14)
C(20)-N(3)-C(17)—C(18)
Ti(1)-N(3)-C(17)-C(I8)
N(3)-C(17)—C(18)—C(19)
N(3)-C(17)-C(18)-C(24)
C(17)—C(18)—C(19)-C(20)
C(24)-C(18)-C(19)-C(20)
C(18)-C(19)—C(20)—N(3)
C(18)—C(19)-C(20)-C(21)
C(17)-N(3)-C(20)-C(19)
Ti(l)-N(3)—C(20)-C(19)
C(17)-N(3)-C(20)-C(21)
Ti(l)-N(3)-C(20)-C(21)
C(22)-N(4)—C(21)-C(20)
C(23)-N(4)-C(21)-C(20)
Ti(1)-N(4)-C(21)-C(20)

286

2.2(3)
4763306)
4767707)
4.7(3)
4.0(3)
178.08(17)
.040)
478.8008)
04(3)
1788508)
09(3)
479.7407)
-2.2(3)
176.3406)
178.44(17)
-3.0(3)
1.0(2)
156.88(14)
-0.6(2)
180.00(17)
00(2)
179.4108)
0.6(2)
469.8(2)
59(2)
461.2703)
171.00(16)
107(2)
77.4209)
-166.31(16)
4538(16)

C(19)-C(20)—C(21)—N(4)
N(3)-C(20)-C(21)-N(4)

C(17)-C(18)-C(24)-C(29)
C(19)-C(l8)-C(24)-C(29)
C(17)-C(18)-C(24)-C(25)
C(19)-C(18)-C(24)-C(25)
C(29)-C(24)-C(25)-C(26)
C(18)-C(24)-C(25)-C(26)
C(29)-C(24)-C(25)-C(30)
C(18)—C(24)-C(25)-C(30)
C(24)-C(25)-C(26)—C(27)
C(30)-C(25)-C(26)—C(27)
C(25)-C(26)-C(27)-C(28)
C(25)-C(26)-C(27)-C(31)
C(26)-C(27)-C(28)-C(29)
C(31)-C(27)-C(28)-C(29)
C(27)-C(28)-C(29)—C(24)
C(27)-C(28)-C(29)-C(32)
C(25)-C(24)-C(29)-C(28)
C(18)-C(24)-C(29)-C(28)
C(25)-C(24)-C(29)-C(32)
C(18)-C(24)-C(29)-C(32)

C(IS)#1-C1(lS)-C(IS)-CI(IS)#1

-161.7(2)
28.4(2)
94.3(2)
849(2)
871(2)
93.7(2)

1.0(3)

4 7752(17)
478.2107)
3.2(3)
55(3)
1787208)
5.20)
-178.08(19)
05(3)
178.3909)
0.0(3)
479.7008)
-0.8(3)
177.7907)
178.9108)
-2.5(3)
0.0

 

Table A7.1 Crystal data for V(NNMe2)(TIP)(dmpe)(I) (49)

Identification code
Empirical formula

Formula weight
Temperature
Wavelength
Crystal system
Space group

Unit cell dimensions

Volume

Z
Density (calculated)

Absorption coefficient

F (000)

Crystal size

Theta range for data collection
Index ranges

Reflections collected
Independent reflections
Completeness to theta = 2500"

Absorption correction

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2
Final R indices [I>23igma(l)]
R indices (all data)

Largest diff. peak and hole

odomsb920_0m

C21H311N3 OP2SV

613.33

173(2) K

0.71073 A

Orthorhombic

Pbca

a = 10.8685(2) A a= 90°.
b = 18.3385(3) A b= 90°.
c = 26.2108(5) A g = 90°.
5224.13(16) A3

8

1.560 Mg/m3

1.782 mm-1
2464

0.28 x 0.12 x 0.10 mm3

2.22 to 2790°.

—12<=h<=14, —24<=k<=24, —31<=l<=33
67170

6199 [R(int) = 0.0556]

100.0 %

None

F ull-matrix least-squares on F2

6199 / 0 / 277

1.019
R1 = 0.0325, wR2 = 0.0627
R1 = 0.0566, wR2 = 0.0701

0.689 and 5.471 e.A-3

288

Table A7.2 Atomic coordinates (X 104) and equivalent isotropic displacement

parameters (A2 X 103) for V(NNMe2)(TIP)(dmpe)(I). U(eq) is defined as one third of

the trace of the orthogonalized Uij tensor

 

 

x y z U(eq)
v0) 7765(1) 4141(1) 3509(1) 22(1)
s0) 8030(1) 5259(1) 3094(1) 29(1)
P(1) 7387(1) 4955(1) 4262(1) 29(1)
3(2) 7751(1) 3304(1) 4266(1) 29(1)
0(1) 8064(2) 3256(1) 3147(1) 26(1)
N(l) 6231(2) 4125(1) 3388(1) 25(1)
N(2) 5130(2) 4083(1) 3203(1) 36(1)
N(3) 9749(2) 4223(1) 3497(1) 23(1)
C(1) 9483(2) 5494(1) 3342(1) 26(1)
C(2) 9885(3) 6216(1) 3371(1) 33(1)
C(3) 10986(3) 6381(2) 3606(1) 37(1)
C(4) 11702(3) 5833(2) 3814(1) 33(1)
C(5) 11327(2) 5111(1) 3782(1) 28(1)
C(6) 10222(2) 4945(1) 3544(1) 24(1)
C(7) 10530(2) 3710(1) 3392(1) 25(1)
C(8) 10208(2) 2978(1) 3250(1) 24(1)
C(9) 11147(3) 2458(1) 3188(1) 33(1)
C(10) 10898(3) 1769(1) 3015(1) 35(1)
C(11) 9693(3) 1584(1) 2891(1) 32(1)
C(12) 8754(3) 2080(1) 2941(1) 29(1)
C(13) 8990(2) 2786(1) 3121(1) 24(1)
C(14) 4677(3) 3368(2) 3052(1) 51(1)
C(15) 4278(3) 4683(2) 3263(2) 54(1)
C(16) 6605(4) 4428(2) 4757(1) 57(1)
C(17) 7287(4) 3746(2) 4857(1) 65(1)
C(18) 6357(3) 5716(2) 4177(1) 57(1)

289

C(19)
C(20)
C(21)
1( 1)

8688(3)
6690(3)
9183(3)
1920(1)

5351(2)
2558(2)
2858(2)
8379(1)

4581(1)
4189(1)
4440(1)
4394(1)

49(1)
43(1)
52(1)
36(1)

 

Table A7.3 Bond lengths (A) and angles (°) for V(NNMe2)(TIP)(dmpe)(I)

 

V(1)-N(1)
V(1)-0(1)
V(1)-N(3)
v0)-s0)
V(1)—P(2)
V(1)-P(1)
8(1)-C(1)
P(1)-C(19)
P(l)-C(18)
P(l)—C(16)
P(2)-C(20)
P(2)-C(21)
P(2)-C(17)
0(1)-C(13)
N(1)-N(2)
N(2)-C(15)
N(2)-C(14)
N(3)-C(7)
N(3)-C(6)
C(1)-C(6)
C(1)-C(2)
C(2)-C(3)

1.698(2)
1.9081(17)
2.162(2)
2.3383(8)
2.5079(8)
2.5078(8)
1.761(3)
1.796(3)
1.803(3)
1.827(3)
1.801(3)
1.817(3)
1.820(3)
1.328(3)
1.293(3)
1.447(4)
1.455(4)
1.298(3)
1.425(3)
1.393(4)
1.396(4)
1.380(4)

290

C(2)-H(2)
C(3)-C(4)
C(3)-H(3)
C(4)-C(5)
C(4)-H(4)
C(5)-C(6)
C(5)-11(5)
C(7)-C(3)
C(7)-H(7)
C(8)-C(9)
C(8)-C(13)
C(9)-C(10)
C(9)-H(9)
C(10)-C(1 1)
C(10)-H(10)
C(1 l)-C(12)
C(1 1 )-H(l 1)
C(12)-C(13)
C(12)-H(12)
C(14)-H(14A)
C(14)-H(14B)
C(14)-H(14C)
C(15)-H(15A)
C(15)-H(ISB)
C(15)-H(15C)
C(16)-C(17)
C(16)-H(16A)
C(16)—H(16B)
C(17)—H(17A)
C(17)-H(17B)
C(18)-H(18A)

0.9300
1.382(4)
0.9300
1.389(4)
0.9300
1.387(4)
0.9300
1.437(3)
0.9300
1.405(3)
1.41 1(4)
1.370(4)
0.9300
1.392(4)
0.9300
1.373(4)
0.9300
1.402(4)
0.9300
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
1.477(5)
0.9700
0.9700
0.9700
0.9700
0.9600

C(18)-H083) 0.9600
C(18)-H(18C) 0.9600
C(19)-H(19A) 0.9600
C(19)-H(19B) 0.9600
C(19)-H(19C) 0.9600
C(20)-H(20A) 0.9600
C(20)-H(203) 0.9600
C(20)-H(20C) 0.9600
C(21)-H(21A) 0.9600
C(21)-H(213) 0.9600
C(21)-H(21C) 0.9600
N(l)-V(1)-O(1) 9340(9)
N(1)-V(1)-N(3) 167.99(9)
O(1)-V(1)-N(3) 8322(8)
N(1)-V(1)—S(1) 9279(8)
0(1)-v0)—s0) 119.53(6)
N(3)-V(1)-S(1) 7903(6)
N(1)-V(1)-P(2) 9755(8)
O(1)-V(1)-P(2) 8274(6)
N(3)-V(1)-P(2) 9346(6)
S(1)-V(1)-P(2) 154.89(3)
N(1)-V(1)-P(1) 8981(8)
0(1)-v0)4>0) 15776(6)
N(3)-V(1)-P(l) 9769(6)
S(1)-V(1)-P(l) 8223(3)
P(2)-V(1)-P(1) 7502(3)
C(1)-S(1)-V(1) 9882(9)
C(19)-P(1)-C(18) 103.56(17)
C(19)—P(1)—C(16) 104.4708)
C(18)-P(1)-C(16) 102.0808)

292

C(19)-P(1)—V(1)
C(18)-P(1)—V(1)
C(16)-P(1)-V(1)
C(20)-P(2)-C(21)
C(20)-P(2)-C(17)
C(21)-P(2)-C(17)
C(20)-P(2)-V(1)
C(21)-P(2)-V(1)
C(17)-P(2)-V(1)
C(13)-O(1)-V(1)
N(2)-N(1)-V(1)
N(1)-N(2)-C(15)
N(1)-N(2)-C(14)
C(15)-N(2)—C(14)
C(7)-N(3)-C(6)
C(7)-N(3)-V(1)
C(6)-N(3)-V(1)
C(6)-C(1)—C(2)
C(6)-C(1)-S(1)
C(2)-C(1)-S(l)
C(3)-C(2)—C(1)
C(3)-C(2)-H(2)
C(1)-C(2)-H(2)
C(2)-C(3)-C(4)
C(2)-C(3)-H(3)
C(4)-C(3)-H(3)
C(3)-C(4)-C(5)
C(3)-C(4)-H(4)
C(5)-C(4)-H(4)
C(6)-C(5)-C(4)
C(6)-C(5)-H(5)

118.510 1)
117.69(11)
108.6201)
103.5606)
104.8507)
102.9009)
112.3901)
117.9900)
113.7301)
135.0106)
168.5(2)
120.3(2)
118.0(2)
119.9(2)
117.1(2)
127.2507)
115.0506)
119.0(2)

1 18.70(19)
122.2(2)
120.3(3)
119.9
119.9
120.3(3)
119.9
119.9
120.3(3)
119.8
119.8
119.4(3)
120.3

293

C(4)-C(5)-H(5)
C(5)-C(6)-C(1)
C(5)-C(6)-N(3)
C(1)-C(6)-N(3)
N(3)-C(7)-C(8)
N(3)-C(7)-H(7)
C(8)-C(7)-H(7)
C(9)-C(8)-C(13)
C(9)-C(8)-C(7)
C(13)-C(8)-C(7)
C(10)-C(9)-C(8)
C(10)-C(9)-H(9)
C(8)-C(9)-H(9)
C(9)-C(10)—C(l 1)
C(9)-C(10)-H(10)
C(1 1)-C(10)-H(10)
C(12)-C(11)-C(10)
C(12)-C(11)-H(1 1)
C(10)-C(11)-H(11)
C(11)-C(12)-C(13)
C(11)-C(12)-H(12)
C(13)-C(12)-H(12)
O(l)-C(13)-C(12)
O(1)-C(13)-C(8)
C(12)-C(13)-C(8)
N(2)-C(14)-H(14A)
N(2)-C(14)-H(14B)
H(14A)-C(14)-H(14B)
N(2)-C(14)-H(14C)
H(14A)-C(14)-H(14C)
H(14B)-C(l4)—H(14C)

120.3
120.8(2)
123.7(2)
115.5(2)
125.0(2)
117.5
117.5
119.0(2)
119.1(2)
121.6(2)
121.4(3)
119.3
119.3
119.2(3)
120.4
120.4
121.0(3)
119.5
119.5
120.5(3)
119.7
119.7
118.6(2)
122.5(2)
118.9(2)
109.5
109.5
109.5
109.5
109.5
109.5

 

N(2)-C(15)-H(15A)
N(2)-C(15)-H(ISB)
H(15A)-C(15)-H(15B)
N(2)-C(15)-H(15C)
H0 5A)-C(15)-H(15C)
H0 SB)-C(15)-H(15C)
C(17)-C(16)-P(1)
C(17)-C(16)-H(16A)
P(1)-C(16)-H(16A)
C(17)-C(16)-H(16B)
P(1)-C(16)-H(16B)
H(16A)-C(16)-H(16B)
C(16)-C(17)-P(2)
C(16)-C(17)-H(17A)
P(2)-C(17)-H(17A)
C(16)—C(17)-H(17B)
P(2)-C(17)-H(17B)
H(17A)-C(17)—H(17B)
P(l)-C(18)-H(18A)
P(1)-C(18)-H(18B)
H(18A)-C(18)-H(ISB)
P(1)-C(18)-H(18C)
H(18A)-C(l8)-H(18C)
H(18B)-C(18)-H(18C)
P(1)-C(l9)-H(19A)
P(1)-C(l9)-H(I9B)
H(l9A)-C(19)-H(19B)
P(1)-C(19)-H(19C)
H(19A)-C(19)-H(19C)
H(19B)-C(19)-H(19C)
P(2)-C(20)-H(20A)

109.5
109.5
109.5
109.5
109.5
109.5

1 10.0(2)

109.7
109.7
109.7
109.7
108.2

111.4(2)

109.4
109.4
109.4
109.4
108.0
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5

295

 

P(2)-C(20)-H(ZOB) 109.5
H(20A)-C(20)-H(203) 109.5
P(2)-C(20)-H(20C) 109.5
H(20A)-C(20)-H(20C) 109.5
H(203)-C(20)-H(20C) 109.5
P(2)-C(21)-H(21A) 109.5
P(2)-C(21)-H(ZIB) 109.5
H(21A)-C(21)-H(2IB) 109.5
P(2)-C(21)-H(21C) 109.5
H(21A)-C(21)-H(21C) 109.5
H(21B)-C(21)—H(21C) 109.5

 

Table A7.4 Anisotropic displacement parameters (A2 X 103) for
V(NNMe2)(TIP)(dmpe)(I). The anisotropic displacement factor exponent takes the form:
-—2 p12[h2a*2U11 +...+2hka* 11* 1112]

 

 

ull u22 {133 {123 1113 ul2
V(l) 19(1) 24(1) 23(1) 0(1) 1(1) 1(1)
8(1) 26(1) 29(1) 33(1) 7(1) 0(1) 4(1)
P(l) 31(1) 29(1) 27(1) -2(1) 4(1) 4(1)
P(2) 36(1) 27(1) 25(1) 2(1) 1(1) —5(1)
0(1) 21(1) 29(1) 28(1) -4(1) 0(1) 2(1)
N(l) 23(1) 29(1) 23(1) 1(1) 1(1) 1(1)
N(2) 19(1) 44(2) 44(2) -3(1) -5(1) -1(1)
N(3) 22(1) 23(1) 25(1) 1(1) 0(1) 0(1)
C(1) 25(1) 29(1) 24(1) 1(1) 7(1) 1(1)
C(2) 39(2) 24(1) 35(2) 3(1) 7(1) 3(1)
C(3) 45(2) 24(1) 41 (2) -2(1) 9(2) -9(1)
C(4) 29(2) 36(2) 35(2) -4(1) 1(1) -6(1)

296

C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(1 1)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
1(1)

25(2)
25(1)
21(1)
23(1)
26(2)
39(2)
42(2)
31(2)
26(1)
44(2)
31(2)
74(3)

130(4)

63(2)
37(2)
42(2)
40(2)
41(1)

28(1)
22(1)
28(1)
23(1)
29(1)
25(2)
23(1)
30(2)
26(1)
67(2)
55(2)
49(2)
35(2)
57(2)
74(2)
35(2)
70(2)
40(1)

32(2)
26(2)
26(2)
27(2)
42(2)
40(2)
31(2)
25(2)
20(1)
41(2)
76(3)
47(2)
30(2)
50(2)
37(2)
51(2)
46(2)
28(1)

-1(1)
-2(1)
1(1)
O( 1)
2(1)
4(1)
-2(1)
-2(1)
2(1)
82(2)
23(2)
-7(2)
0(2)
81(2)
81(2)
5(2)
34(2)
3(1)

5(1)
5(1)
-3(1)
-1(1)
4(1)
1(1)
4(1)
3(1)
2(1)
0(2)
42(2)
32(2)
27(2)
41(2)
0(2)
0(2)
-6(2)
0(1)

0(1)
-2(1)
0(1)
1(1)
4(1)
9(1)
-2(1)
-5(1)
1(1)
49(2)
7(2)
-5(2)
4(2)
31(2)
0(2)
-8(1)
-7(2)
41(1)

 

Table A7.5 Hydrogen coordinates (X 104) and isotropic displacement parameters (A2 X

103) for V(NNMe2)(TIP)(dmpe)(I)

 

 

y 2 U(€61)
H(2) 9410 6587 3230 39
H(3) 1 1247 6863 3626 44
H(4) 12438 5949 3975 40
H(5) 11812 4742 3919 34
H0) 11363 3824 3410 30

H(9)
H00)

H0 1)

H02)

H(14A)
H(14B)
H(14C)
H(15A)
H053)
H(15C)
H(16A)
H063)
H(17A)
H073)
H(18A)
H083)
H(18C)
H(19A)
H093)
H09C)
H(20A)
H(203)
H(20C)
H(21A)
H(213)
H(21C)

11953
11528

9521
7955
5348
4068
4317
3815
3726
4727
6554
5775
6772
8012
6279
5564
6679
9032
9298
8430
6735
6900
5869
9072
9816
9418

2584
1429
1117
1946
3080
3423
3129
4618
4695
5133
4713
4313
3416
3854
5977
5540
6036
5729
4981
5553
2244
2286
2745
2596
3218
2524

3267
2980
2772
2854
2924
2790
3341
3572
2977
3280
5068
4647
5052
5059
4492
4072
3919
4372
4640
4901
4481
3888
4156
4754
4483
4176

39
42
38
35
76
76
76
81
81
81
68
68
78
78
85
85
85
74
74
74
64
64
64
78
78
78

 

298

Table A7.6 Torsion angles (°) for V(N'NMe2)(TIP)(dmpe)(I)

 

N(1)-V(1)-S(1)-C(l)

O(1)-V(1)-S(1)—C(1)

N(3)-V(1)-S(1)-C(1)

P(2)-V(1)-S(1)-C(1)

P(1)-V(l)-S(l)-C(1)

N(1)-V(1)-P(l)—C(19)
O(l)-V(1)-P(1)-C(l9)
N(3)-V(1)-P(l)—C(l9)
S(1)—V(1)-P(1)-C(19)
P(2)-V(l)-P(1)—C(19)
N(1)-V(1)-P(l)-C(18)
O(1)-V(l)-P(1)-C(18)
N(3)-V(1)-P(1)—C(18)
S(1)-V(1)—P(I)-C(18)
P(2)-V(1)-P(l)-C(18)
N(1)-V(1)-P(1)—C(16)
O(1)-V(1)-P(1)-C(16)
N(3)-V(1)—P(1)-C(16)
S(1)-V(l)—P(1)-C(16)
P(2)-V(l)-P(l)-C(16)
N(1)-V(1)-P(2)-C(20)

O(l)-V(1)-P(2)—C(20) .

N(3)-V(1)-P(2)-C(20)
S(1)-V(1)-P(2)-C(20)
P(1)-V(1)-P(2)-C(20)
N(1)—V(1)-P(2)-C(21)
O(1)-V(1)-P(2)-C(21)
N(3)-V(1)-P(2)-C(21)
S(1)-V(1)-P(2)-C(21 )

163.5201)
400.9901)
-25.34(11)
49.0602)
7410(9)
471.6106)
899(2)
4.0205)
-78.77(14)
9052(14)
45.7107)
444.2(2)
124.8706)
47.1305)
443.5806)
69.5106)
890(2)
419.9005)
162.3504)
8836(14)
3893(14)
-53.56(13)
-l36.27(13)
152.4103)
126.6902)
159.3406)
6685(15)
45.8605)
-87.18(16)

P(1 )-V( 1 )-P(2)-C(2 1)
N(l)-V(1)-P(2)-C(17)
O(l)-V(1)-P(2)-C(17)
N(3)-V(1)-P(2)-C(17)
S(1)-V(l)-P(2)-C(17)
P(1)-V(l)-P(2)-C(17)
N(1)-V(1)-O(1)-C(13)
N(3)-V(1)—O(1)-C(13)
S(1)-V(l)-O(1)-C(l3)
P(2)-V(1)-0(1)-C(13)
P(1)-V(l)-O(1)-C(l3)
O(1)-V(1)-N(1)-N(2)
N(3)-V(1)-N(1)-N(2)
S(1)-V(l)-N(l)—N(2)
P(2)-V(1)-N(1)-N(2)
P(1)-V(1)-N(1)-N(2)
V(l)-N(1)-N(2)-C(15)
V(l)-N(1)-N(2)-C(14)
N(1)-V(1)-N(3)-C(7)
O(l)-V(1)-N(3)-C(7)
S(1)-V(1)-N(3)-C(7)
P(2)—V(1)-N(3)-C(7)
P(1)-V(1)-N(3)-C(7)
N(l)-V(1)-N(3)-C(6)
O(1)-V(1)-N(3)-C(6)
S(1)-V(1)-N(3)-C(6)
P(2)-V(1)—N(3)-C(6)
P(1)-V(1)-N(3)—C(6)
V(1)-S(1)-C(1)—C(6)
V(1)-S(l)-C(1)-C(2)
C(6)-C(1)—C(2)-C(3)

4 12.9004)
-80.01(18)
-172.49(18)
104.8008)
3348(19)
776(17)
465.1(2)
265(2)
99.8(2)
579(2)
573(3)
45.9(10)
27.3(13)
74.000)
429.0(10)
156.2(10)
425.5(9)
69.5(11)
894(5)
45.1(2)
437.0(2)
671(2)
142.5(2)
81.6(5)
155.8508)
3394(16)
421.8907)
4656(17)
203(2)
455.8(2)
4 5(4)

300

S(1)-C(1)-C(2)-C(3)
C(1)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-C(5)
C(3)-C(4)-C(5)-C(6)
C(4)-C(5)-C(6)-C(1)
C(4)-C(5)-C(6)-N(3)
C(2)-C(1)-C(6)-C(5)
S(1)-C(1)-C(6)-C(5)
C(2)-C(1)-C(6)-N(3)
S(1)—C(1)-C(6)-N(3)
C(7)-N(3)-C(6)-C(5)
V(1)-N(3)-C(6)-C(5)
C(7)-N(3)-C(6)-C(1)
V(1)-N(3)-C(6)-C(1)
C(6)-N(3)-C(7)-C(8)
V(1)-N(3)-C(7)-C(8)
N(3)-C(7)-C(8)-C(9)

N(3)-C(7)-C(8)-C(13)
C(13)-C(8)-C(9)-C(10)

C (7)-C(8)-C(9)-C(1 0)

C(8)-C(9)-C(lO)—C(1 1)
C(9)-C(10)-C(1 1)-C(12)
C(10)-C(11)-C(12)-C(13)
V(1)-O(1)-C(13)—C(12)
V(l)-O(1)-C(13)-C(8)
C(11)-C(12)-C(13)-O(1)
C(1 1 )-C(12)-C(13)-C(8)
C(9)-C(8)-C(13)-O(1)
C(7)-C(8)-C(13)-O(1)
C(9)-C(8)-C(13)-C(12)
C(7)-C(8)-C(13)-C(12)

174.6(2)
03(4)
07(4)
5.5(4)
5.7(4)

479.1(2)
1.7(4)

474.5(2)

479.7(2)
4.1(3)

404(4)
147.7(2)
141.1(2)
-30.8(3)
169.3(2)
15(4)
474.6(3)
1 1.7(4)
4 0(4)
474.9(3)
08(4)
5.1(4)
5.3(4)

160.1 1(19)
825(4)
177.7(2)

02(4)

4769(2)

52(4)
05(4)
174.2(2)

301

C(19)—P(1)-C(16)-C(17)
C(1 8)-P(l)-C(16)-C(17)
V(l)-P(1)-C(16)-C(l7)
P(l)-C(16)-C(17)-P(2)
C(20)-P(2)-C(17)-C(16)
C(21)-P(2)-C(17)-C(16)
V(1)-P(2)—C(17)-C(16)

45.9(3)
176.4(3)
515(3)
-44.8(4)

403.4(3)
148.6(3)
198(3)

 

302

APPENDIX B

Kinetic reaction plots

Figure B1.1 Kinetic plot for Run 1 with 10% Ti(dap)2(NMe2)2 (l).

 

601
1 Exp 918 J
50- 10% Ti(dap)2(NMe2)2 W
1"
4O ‘ a Data: Data1_B
. If" Model: myeqn1
_ .X‘ Weighting:
17.”, 3O 7 y No weighting
3. - " Chi"2/DoF = 0.91855
5° 20_ n!" R42 = 0.99695
9’ yO 0301921057604
,‘ yinf 56955621061079
1° ‘ ‘4 k 0005041000017 min'1
0 I‘ k 0.84E-4s'1

 

 

 

 

 

' 1 ' 1 ' I ' t ' I ' lfi'
0 100 200 300 400 500 600
time (min)

303

Figure 81.2 Kinetic plot for Run 2 with 10% Ti(dap)2(NMe2)2 (l).

 

   

 
 

 

 

 

 

10% Ti(dap)2(NMe2)2
,
50-
Data: Data1_B
Model: myeqn1
45 _ Weighting:
U /- . .
T2 /' y No welghtlng
'3 40 1,..-' Chl42/ool: =O.36175
o\ ‘ .9 R42 = 0.99186
.6 yo 28343171040379
35 If yinf 556821025831
_ / _
4 q” k 000552100002 min 1
I1" -1
30_ k 0.9254 s
l I I l I I r I
0 100 200 300 400 500 600
time (min)

Figure B1.3 Kinetic plot for Run 3 with 10% Ti(dap)2(NMez)2 (l).

 

 
 

 

   

 

 

 

 

55-
Exp 929
50 _ 10% Ti(dap)2(NMe2)2
45-
‘ Data: Data1_B
40 ‘ Model: myeqn1
' Weighting:
2 35‘ f. y No weighting
.g ‘ II Chi"2/DoF = 0.72942
05 30‘ n" R42 = 0.99145
‘ .1 yo 15.186 :10
25' ,_ yinf 50987571020852
20 .. ". k 000791000017 min”1
. -1
- k 1. E
15_ I 32 -4 s
10 I I I I ' I I ' I 1
0 100 200 300 400 500 600
time (min)

304

 

Figure B2.l Kinetic plot for run 1 with 10% 36.

 

 

 

 

 

 

 

  

  

 

 

 
 

 

 

70: Exp 934
65 _ 10% Ti(htdrazido)
60 ~
1
55 1 , Data: Data1_B
. I. Model: myeqn1
% 50- I. Weighting:
'5. 1 f y No weighting
°\° 45 - Chi"2/DoF = 0.05563
‘ I’ R"2 = 0.99958
40 7 ." yO -1.37066 1051344
‘ p” yinf 71.6871 10.16031
35 - i _1
~ i k 0.00606 min 10.00007
30: ' l< 1.01E-4 s'1
25 I r I I I ' 1
1 00 200 300 400 500 600
time (min)
Figure 82.2 Kinetic plot for run 2 with 36.
80 -
Exp 938
10% Ti(htdrazido)
70 -
60 -
Data: Data1_B
Model: myeqn1
% 50- 1' Weighting:
'3 y No weighting
o\° Chi"2lDoF = 0.05563
40 - R"2 = 0.99967
:1 y0 2.52643 10.39247
.i yinf 76.58863 10.17972
30 ' .1" k 0.00534 min'1 10.00005
k 0.89E-4 s'1
20 I T I I I j
0 100 200 300 400 500 600
time (min)

305

 

Figure 32.3 Kinetic plot for run 3 with 10% 36.

  

 

  
 

 

 

 

 

65 ‘ Exp 941
60 _ 10% Ti(hydrazido)
55 -
50 _ Data: Data1_B
. Model: myeqn1
E 45 - Weighting:
.1; . F. y No weighting
°\o 40 - Chi"2/DOF = 0.03185
- R"2 = 0.99975
35 - F yO -1 .19282 10.3297
30 . ." yinf 88.20252 10.11031
. .r' k 0.00606 min'1 10.00005
25 ' " k 1.01E-4 s‘1
20 1 I l I I I I
0 100 200 300 400 500 600
time (min)

Figure B3.1 Kinetic plot for run 1 with 36 + 10 MezNNHz reaction.

% yield

 

 

 

 

Exp 953
100 ' Ti(hydrazido) + 10 MezNNHZ ;/.
1 /.
/,x
90 "" .//.
1 I”. Data: Data1_B
80 _ .r ’ Model: myeqn1
/ u / Weighting:
1 p y No weighting
)- Chi"2/DoF = 010573
70 ‘ / R"2 = 0.99951
yO 51740181031915
r.” yinf 132.385551277365
6° ‘ / / k 000582100003 min'1
I
k 0.94E-4 s'1
50 I I ' I f I ' I ' I ' I ' I 1 I ' I
o 20 4o 60 80 100 120 140 150 180
time (min)

306

 

 

 

Figure B3.2 Kinetic plot for run 2 with 36 + 10 MeZNNHz reaction.

 

 

 

 

 

 

100 - EXP 954 a
Ti(hydrazido) + 10 MeZNNHz yu}
9”
90 - ,,r’
,I
A
i ’ Data: Data1_B

80 " _/ Model: myeqn1
% ,l ' Weighting:
‘3. /' No weighting

. Y
e" 70 - /' chi42/ooF = 0.60629
f R42 = 0.99778
[I yO 4500011069602
50 1 gr yinf 120664621283257
,5 k 0006561000046 min‘1
50 - a k 1.09E-4 s‘1
I ' I ' I ' I ' I
o 50 100 150 200
time (min)

Figure 83.3 Kinetic plot for run 3 with 36 + 10 MeZNNHz reaction.

 

 

 

 

 

 

100 Exp 957
90 -1
l’yi
y Data: Data1_B
A" Model: myeqn1
1?; 8° 7 ./ Weighting:
'5. . .4 ‘ y No weighting
°\° ./ Chi"2/DoF = 1.03214
70 - ./ R42 = 0.9936
yO 57.28210
/' yinf 11008981174162
6° ‘ _ k 0007891000047 min‘1
k 1.32E-4 s'1
50 I ' I ' I - I ' I I j
0 50 100 150 200 250
time (min)

307

Figure 84.1 Kinetic plot for run 1 with 36 + 10% Hdap reaction.

80—

70-

 

Exp 966
10% Ti(hydrazido) + 10% Hdap

 

 

 

 

 

Data: Data1_B
Model: myeqn1
‘, Weighting:
p y No weighting
." Chi"2/DoF = 1.43309
. :’ R42 = 0.99431
. yO 14.44110
.5 yinf 75628391032089
5 k 0007161000013 min'1
1 ' k 1.19E-4 s'
r ' I ' I I ' I I r 7
o 100 200 300 400 500 600
time (min)

Figure 84.2 Kinetic plot for run 2 with 10% 36 + 10% Hdap reaction.

 

' Exp 989
50 _ 10% Ti(hydrazido)+10%Hdap

  

 

   

 

 

 

50 ‘ Data: Data1_B
Model: myeqn1
Weighting:
2 40 ' y No weighting
31; .d Chi"2/DoF = 0.12058
o\° ii R42 = 0.99922
30 - .1 y0 13589641021135
5' yinf 62368391012546
I
20 ,5 k 0006251000006 min”1
." k 1.04E-4 s'
10 I I r I I I I I fi
0 100 200 300 400 500 600
time (min)

308

 

 

Figure 34.3 Kinetic plot for run 3 with 10% 36 + 10% Hdap reaction.

 

 

  

 

 

 

 

 

 

 

 

 

 

309

- Exp 996
70 _ 10% Ti(hydrazido) + 10% Hdap
60 -
Data: Data1_B
5o _ Model: myeqn1
If Weighting:
% y No weighting
'5. 40- i. Chi"2/DoF = 0.30651
5° ,5 R42 = 0.99854
1'- yO -24.5461111.08498
30 7 [,1 yinf 6938436101769
5." k 0008021000011 min'1
20- .- -1
q k 1.34E-4 s
10 r I I I I I I fl
0 100 200 300 400 500 600
time (min)
Figure 85.1 Kinetic plot for run 1 with 10% 37.
25 -
Exp 978
10% 37
20- ,4"
a“.
15 ' fin; Data1_B
I
.0 Model: myeqn1
E; Weighting:
3; 10 - y No weighting
°\ Chi"2/DoF = 0.04691
R42 = 0.99894
5 - _- y0 -11.8033210.44029
ff.- yinf 199.2360716462531
0 .. k 000029100001 min'1
k 4.8E-6 s'1
I I I I I j
200 300 400 500 600
time (min)

 

Figure 86.1 Kinetic plot with 15% Ti(dap)2(NMe2)2.

 

 

 

 

 

7 _
0 Exp 1017
. 15% Ti(dap)2(NMe2)2W
60 ‘ n’i
5-
.5,- Data: Data1_B
50 _ ' Model: myeqn1
p, Weighting:
‘2 u . .
,1, . u y No welghtlng
f; .1 Chi"2/DoF = 0.54438
°\ 40 - y” R"2 = 0.99457
y" yo 23.5 10
i yinf 66038711017799
30 - k 0010711000018 min"1
. R 1.7954 s'1
20 I ' l I I I t r
0 100 200 300 400 500
time (min)

Figure 86.2 Kinetic plot with 5% Ti(dap)2(NMe2)2.

 

   

  

 

 

 

 

 

50-
Exp 973
5%) Ti(dap)2(NMe2)2
4o-
30 _ Data: Data1_B
'0 Model: myeqn1
E9 Weighting:
> y No weighting
a" 20- Chi"2lDoF =0.16589
1" R42 = 0.99877
-' yO 3072311021002
10_ "l yinf 49633841033007
j k 0003651000007 min'1
k 0.61E-4s-1
O I ' I I I ' I I ' I fl
0 100 200 300 400 500 600
time(min)

310

 

Figure 86.3 Kinetic plot with 2.5% Ti(dap)2(NMe2)2.

 

  

 

 

   
  

 

 

22 -
Exp 975
20 - 2.5% Ti(dap)2(NMe2)2
18 -
16 j Data: Data1_B
U 14 _ Model: myeqn1
E , Weighting:
‘5. 12 _ y No weighting
8° . Chi"2/DoF = 0.01994
10 1 R42 = 0.99923
1 yo 1.530831009715
8 7 yinf 29313431039405
6 - I k 0002051000005 min‘1
4; , k 0.34E-4 s'1
I ' I . I I ' I fl
0 100 200 300 500 600

time (min)

31]

 

APPENDIX C

Figure C.1 1H and 13C NMR spectra of compound 2.

 

 

 

 

O
x0
N
Up
N—
/
z n J
I l 1 -. II
‘I"'TIfT"T‘—r"I'"'I""I"fi'Ir'firI""I'rT'I
9 8 7 6 5 4 3 2 100m
0.95 1.05 3.00 4.20 9.01
[.40

 

 

 

 

 

 

 

 

 

240 220 200 I80 I60 I40 120 100 80 6O 4O 20 0 ppm

312

Figure C.2 1H and 13C NMR spectra of compound 4.

 

 

 

 

 

 

 

 

 

 

 

/—\
~—— / NH
\ NH /
.1 lLil -.....ipt l
I I T I 1I I I‘r' I I'IIIFrI'IT I 7IT I 7
ll 10 9 8 7 6 S 4 3 2 1 ppm
[.55 1.93 1.97 3.86 6.0I
L78 3.95
~--— / NH
\ NH /
e. I . I , , , , . , . , “1--.... ”W,“ .....,.W....,.........,....
200 I 80 I60 I 40 120 I 00 80 60 40 20 ppm

Figure C.3 ]H and 13C NMR spectra of compound 5.

 

 

 

 

 

I I! I I. I!
ll 1 1 I II 1.
W I 77 Ijj I I jrr I ll"'I"'_'_I" I I 'I""I""I""I
12 10 8 6 4 2 0 ppm
1.97 1.85 2.02 2.24 2.07 6.00
L93 12.12 2.11

\ NM62

\ N \ \\\ N M62

 

 

 

 

 

 

IIIIIfiTTIITYITIY—T—l—TIIIIII[I'VIIIIIIITII[11rTIUY]IIIYIIITrlYITIIIIleUTVVIYIIIITYIIlIIUIITrFIIIIVIl'lIllllTr

200 I 80 I 60 I 40 I 20 I 00 80 60 40 20 ppm

314

Figure C.4 1H and 13Cctra of compound 7.

 

 

 

 

 

HN.
11'
/C\/\/
l
# __A,__ _1 ,_ .1
FT 1 [IITIIIIIIIYIfiII’IIITITTTTTI I 1:,“in 1 IIr I | I
12 IO 8 6 4 2 0 ppm
3.10 0.91 0.98 2.12 3.00 3.68
I.04 2.43 2.54
HN.
i?

 

 

 

 

 

 

 

 

 

 

240 220 200 I80 I60 I40 120 I00 80 60 40 20 0 ppm

3I5

Figure C.5 1H and 13C NMR spectral data of compound 13 and 14.

21

i
O
O

 

 

 

10 9 8 7 6 5 4 3 ppm
0.89 0.92 420123335 100
057 3.34 1.12 1.24 3.39

13 14
II .1

“Ii-”,5. , [v I in.”

240 220 200 I 80 I60 140 120 100 80 60 40 20 0 ppm

\ZI

 

 

.11]. i,....,....,. "I , I I ,nul

3I6

Figure C.6 1H and 13c NMR spectral data of compound 15.

 

 

 

 

 

 

H
N
/
l
1111 l l ‘
mm...”w...m”....,....,....,T...,...mm“...,..r.T....,.........,.....
'l2 10 8 6 4 2 0 ppm
0.82 0.86 1.95 2.78 5.21
0.911.79 1.96 9.00
H
N
/
l

 

 

 

 

 

 

 

 

 

 

240 220 200 180 I60 140 l20 100 80 60 40 20 0 ppm

3I7

Figure C.7 1H and 13C NMR spectral data of compound 17.

 

 

 

 

 

1...,1..-...,...........-..,.........,.........,e....e..1,...
I211l0987654321ppm
2.15 0.94 2.14 2.15300
1.95 2.20
,N
N

 

 

 

 

 

 

 

 

 

W1. 71.... we fl ” 1 ‘ .3::t,._ .0 7.1 42:”
WTVI'IIIIIYITII'TIITrIIII'IIIIIIIIIIII'TWT—II'TWTITTIIIIIII I I l I I ‘IIIIIITTITI—YFIT‘IIITI ] I I I I l

 

3l8

Figure C.8 1H and 13C NMR spectra of compound 20.

Z]:

NH2

 

 

III II Ii
11 1. A1
IIII IIII IT IIII IIIIIIIII II

12 ll 10 9 8 7 6 5 4 2 ppm
0.92 1.09 2.02 2.98
l.04 2.36 2.04 2.25

NH2

 

 

 

240 220 200 180 I60 I40 120 I00 80 60 40 20 ppm

3I9

Figure C.9 1H and 13C NMR spectra of compound 21.

 

 

 

 

 

H
N
/
H3O
-1. . .1
"'I"“l"r'1""I""l""I""l' l""l""I I' I""
12 ll 10 9 8 7 6 5 4 3 2 1 ppm
0.73 0.96 1.92 3.00 3.10
0.890.90 3.00 2.25
H
N
/
H3C
l ’
..Jh l -
l l""l""l""l I l I I I l 'lll'l' 'l'l 'l"""'|' ""l""' "I‘ I I I' l
240 220 200 I80 160 140 120 100 80 6O 40 20

320

Figure C.10 1H and 13C NMR spectra of compound 24.

 

 

 

 

 

N,N
l/

Il I ' LL

l . . .
”HUM.,.ra.r.....m..,....,....,.........,.........1....,....,.........,...r,

l2 IO 8 6 4 2 0 ppm

4.07 0.53 1.00 3.00 4.0] 3.34

0.94 0.53 1.07109
N,N
I/

 

 

 

 

 

 

 

 

 

 

 

 

32]

Figure C.11 ]H and 13C NMR spectra of compound 25.

 

 

 

N,N
I /
J I
12 10 8 6 4 2 0 ppm
401 0.92 2.99 4.12
1.08 1.95 2.02 2.92
N/N

 

 

 

 

240 220 200 I80 160 I40 120 100 80 60 40 20 0 ppm

322

Figure C.12 1H and 13C NMR spectra of compound 35.

 

 

 

 

 

IIIIIrrrTIIIIIIIIIIITIIITIWIIfiIrIIIIIIIITII'IIIIIITITIIIIIIIIIIIIIIIIIIIIIIIIIIII

121ll09876543210-l ppm

1.811.09 0.75 7.32 2.26 2.87
l.2l 6.42 2.51 3.00

 

 

 

 

 

 

II].IIFTIIIIIII’IITI’IIIII‘II‘IIII|IIIIITIITrYIIIIIIIIIIIIIIIIIIIIITIIIIIIIITWWITIIIIIIITIIIIIIIIIIII'IIIIIII'IIIIIIIIIIIIIIIIYII

323

Figure C.13 1H and 13C NMR spectra of compound 38.

 

 

 

 

 

 

.1101 LimLLJL -_

rIlI[IITI'IfiTITIIIIIITIIIIIIITITjiniTTrjIIIIIIIIIIIITjTTIIIIlrfi

l 0 9 8 7 6 5 4 3 2 l -0 ppm

1.08 l.04 1.07 3.513.28 3.15 3.51
3.2] 3.02 3.59 3.35

 

 

 

-1 -14 1 A- 21in MIW .1 LIL-1_.L. I l _ -2.

fi-Y f“ fl r. rv—v v-v- V —r r r.—- 'TVV

 

IIFTTIIIIIIIIIII]IIIIIITI—IITIIIIIIII[IIWTIIIIIIIT‘I‘IT—III—IITIIIIITITTWWTT'IfiIIIIIIIIIIIIIIrIjllIIlfiTI

200 I 80 I60 I40 120 I 00 80 60 40 20 ppm

324

Figure CM 111 and 13C NMR spectra of compound 39.

 

 

 

 

 

T FTW’II T} I] lYl’TI TrT I]! VT 1]! [I If TT' 1' TI YT IV 1! Fri 171’]! 11 Ill TT‘rTjiTT I] T] '1] TV Y1 III II]

1.20 LII 0.97 2.20 2.47 3.94
2160

 

 

 

 

 

 

 

 

IllYIIITIITTIIllIIY]YIFIITIYU]ITTII‘IIYIIIII]IYYY]IYYYIYTYI[IIII]YIYI1IYFFIrY'IITFIIITTTVIIIIIIITTTTTTWTIYTTTTTT77TTYIIIIIIU 1‘11 '11!

240 220 200 I80 I60 I40 120 100 80 60 40 20

325

Figure C.15 1H and 13C NMR spectra of compound 40.

 

 

 

A All‘ -1-
IIITYTT 11" VIII IrTYIIYIIT'WIFIIr'

 

WW I I l ‘I“"l""l""T‘H'IHHIH‘T
l4|31211|0987654321ppm
0.91 2041.03
1.86 2.05
N’N
I/

 

240 220 200 180 I60 I40 l20 I 00 80 60 40 20

326

 

Figure C.16 1H and 13C NMR spectra of compound 41.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

N,N
' /
’ I
H_ L l
I TI Th I I I I ‘IFIfI I l""IrrT Fr
II 10 9 s 7 6 5 4 3 2 1 0 ppm
0.92 1.00 2.37 2.64 3.51
5.07 2.62
N’N
I /
n l W A W W
200 I80 I60 140 120 100 80 60 4o 20 ppm

327

Figure C.17 1H and 13C NMR spectra of compound 42.

w

 

 

 

 

 

 

 

If I 'FI I'III'IIIHII'I'II'I'III'I'ITIIII'I'II'IHI'fIII'If
ll 10 9 8 7 6 5 4 3 2 I 0 ppm
0.76062 2.53 1.84 3.08

1.521.13 0.72 2.22 3.15

 

 

 

 

JIIJJLILHHJJJL[1:11.I..su.n1ub.~h m.“- m.£u1md 1]: Ii .11 1t.IL1..~L._uI.I . u ' .. .. . ..L1 p. . I

200 1 80 160 140 120 100 80 60 40 20 ppm

328

Figure C.18 1H and 13C NMR spectra of compound 44.

MezN

\ZI

 

 

A I 1 1: . L.
.....,..I .....l. ...I..... .1......H.1.r.ry,.

 

l I 10 9 8 7 6 5 4 3 ppm

0.80 1.02 0.98 2.01 6.02 3.15
2.04 6.28

M62N

\ZI

 

 

 

llllII]lll!]llll|vllll1lvv[IVIIIVIIIIYIIVIIIll1IIIIIIIII|IIIV1IIIIIIIIIIIIIIlllvIIIInl|ll|llllII|llllllllllvvvtlllrvIYl11T

220 200 180 160 140 120 100 80 60 40 20 0 ppm

329

Figure C.19 1H and 13C NMR spectra of compound 45.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Me
Me 1
Me NMez
\ NII...1|.i‘.\HNMeZ
N/1\NMe
M82 N
\ /
Me
Me
II 4
Me 2, [1 ,1
.mr-.. ,.........,.WTW..,....,...-,....T....”my...”..........,....,.-...
12 10 8 6 4 2 0 ppm
3.90 1.89 12.00 6.15
1.95 3.71 115612.19
Me
Me
Me NMe;
\ NII.,..'|.i,.\I\NMez
N/|\NMe2
M82 N
\ /
Me
Me
Me
Wuflww

 

fiiVI1111]]IIIllYthTYTTjrYYrTYTTITIYYTIIIIIYIIIIIYTTIIIIII1IIllIYTI[YITITTWTTITTIYIIIIYITVIYIYIIUIIYTTIIIIYTIIII]IIII]VIIYIYIVU]I'll]

240 220 200 180 160 140 120 100 80 60 40 20 0 ppm

330

 

 

Figure C.20 IH and 13C NMR spectra of compound 46.

 

 

 

 

 

 

S|iMe3
CES
,SiMe
N o 3
H
I .1../ 4
LL“ __ A _._ ‘1JJ
YIYIIjIIIIIIIIYTIYIYIIIIj'II'U'IIYIIlj'UIIIIIYIUIYIltTTIrI'rTll'IIIIYIYrI'
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.78 2.092.05 8.98
2.112.07 9.00

 

 

 

 

 

220 200 180 160 140 120 100 80 60 40 20 0 ppm

331

   

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