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CHEMISTRY OF LOW VALENT METAL CARBONYL,
NITRILE, AND HALIDE COMPLEXES WITH A BULKY
OXYGEN FUNCTIONALIZED PHOSPHINE LIGAND

By

J ui-Sui Sun

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements

for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1994

ABSTRACT

CHEMISTRY OF LOW VALENT METAL CARBONYL,
NITRILE, AND HALIDE COMPLEXES WITH A BULKY
OXYGEN FUNCTIONALIZED PHOSPHINE LIGAND

By

J ui-Sui Sun

There has been considerable interest in the chemistry of tertiary
phosphines with transition metal complexes due to the important role that
phosphines play in homogeneous catalysis. Ether-phosphine ligands are of
special interest because weak metal-ether interactions have been correlated
with increased reactivity at the metal center. This has been demonstrated
in the selectivity enhancement in the oligomerization of ethane, and in
stereoselective hydrogenation, hydrosilylation, and hydroformylation.
Unusual features of the ether-phosphine compound tris(2,4,6-trimethoxy—
phenyl)phosphine, (T MPP), are its high basicity, which increases the
reactivity of the metal center toward n—acceptors, and the presence of
multiple ether substituents, which can participate in various bonding modes
(r1l to n3) and can accommodate a variety of nuclearities (monometallic to
tetrametallic).

Fixation and activation of phosphine transition metals with small
molecules such as C02, N2, H2, 802, CO, and 02 are topics of considerable
interest in areas as diverse as biochemistry, catalysis, and pollution control.

This work first focuses on the syntheses and reactivity studies of fluxional

metal phosphine complexes (n3-TMPP)M(CO)3 (M = Cr, Mo, W). By the
use of a flexible, bulky ether-phosphine (T MPP), the first series of tri-,
tetra-, and penta-carbonyl metal complexes possessing only one phosphine
ligand was structurally characterized from the reaction of (113-
TMPP)M(CO)3 with CO, wherein the chelating TMPP ligand acts as a n3,
I12, and n1 ligand to the metal center respectively.

The reactions of fully solvated late transition metal complexes with
TMPP under various conditions produce homoleptic bis-phosphino-
phenoxide metal complexes M(TMPP-0)2 (M = Co, Ni, Pd, Pt) and a bis-
phosphine complex [Pd(TMPP)2][BF4]2. Despite the fact that most Pd(II)
complexes typical exhibit square-planar geometries, the complex
[Pd(TMPP)2][BF4]2 exhibits the shortest axial contact (Pd-Oaxial) to date
for octahedral Pd(II) complexes.

The discovery of an interesting ferromagnetic compound [H-
TMPP]2[Fe2C16] from the reaction of FeCl3 with TMPP led to
investigating this area. Syntheses and magnetic studies of a series of
dinuclear complexes containing [Fe2C16]2' unit with a variety of salts as

well as an extended studies of a polynuclear ferrous compound

Fe4Clg(THF)6 are presented.

To my husband (Yu—Ju) and my parents (Y u-Chen and Jui-Liu)

ACKNOWLEDGEMENT

The work in this dissertation can not be done without the assistance
and support of a lot of people. First, I would like to thank my advisor,
Professor Kim R. Dunbar, for her wise guidance, support, and helpful
discussion. It is because her enthusiasm and permission to inspire me and
allow me to get as many results as I can. Though they may not as specific
as she likes in order to complete a decent story, but I do my best to put a
stamp on our territory due to the strong competition. I also like to thank
my committee: Professor M. G. Kanatzidis, Professor J. E. Jackson and J.
L. McCracken for their helpful comments, as well as Professor D. G.
Nocera for his advice as a second reader on my defense. I would also like
to thank Dr. D. Ward for his assistance on single X-ray crystallography.

I would like to take this opportunity to thank Prof. George Christou
for giving a short but compact class on Magnetism. It is a good start to
help me to understand the basic things in this field. It is because that I can
discuss the magnetic properties of my compounds with Prof. Dunbar at the
end of my career at Michigan State University. This is an unforgettable
experience for me to be able to discuss "magnetism" with my advisor,
which I have ever thought that it would be possible. I cherish the
friendship received from all the members in Dunbar group from the first
unique generation, Sue-Jane, Steve, Laura, Stuart, Anne, Stacey, John, and
Julie, to the young people now. Stuart's help and friendship is always
being missed. I could not have learned so much about American culture

without Gary's help. I miss the coffee break we had at Room 416 when

Stuart and Susan were around, even though Gary is the only one who does
not know how to enjoy it. Of course, Sean is always there and makes
comments about everything verbally or by his unique face expression even
though we sometimes could not understand what he is trying to say. I
thank young fellows, Kemal, Calvin, and Shannon, for their friendships
and I appreciate the things I have learned from you folks while teaching. I

\II

also like to say "doo shop to my dear friends who I have not mentioned
yet, especially those at Taiwan for their friendships and encouragement.
Most importantly, I want to give my deepest appreciation to my

parents and my husband for their great support and understanding.

TABLE OF CONTENTS

page
LIST OF TABLES ..............................................................................
LIST OF FIGURES ............................................................................
LIST OF COMPOUNDS ....................................................................
CHAPTER I. INTRODUCTION ...................................................... 1
1. Transition Metal Complexes with Fuctionalized
Phosphines ............................................................................. 2
2. Tris(2,4,6—trimethoxyphenyl)phosphine (TMPP) ................... 2
3. Chemistry of TMPP with Transition Metal
Complexes ............................................................................... 6
A. Group VI Metal Carbonyls .......................................... 6
B. Late Transition Metal Complexes ................................ 11
C. Metal Halides Complexes ............................................ 13
List of References ........................................................................ 14
CHAPTER II. SYNTHESES AND REACTIVITY STUDIES OF
THE FLUXIONAL PHOSPHINE COMPLEXES » ‘
(n3-PR3)M(CO)3 (R = 2,4,6—Trimethoxyphenyl,
M = Cr, Mo, W) ........................................................ 18
1. Introduction ............................................................................. 19
2. Experimental Section .............................................................. 20

vii

A. Physical Measurements ................................................. 20

B. Synthesis ........................................................................ 2O
(1) Preparation of (nZ-TMPP)Mo(C0)4 (2) ................ 21
(i) Purging of 1 with N2 and H2 ......................... 21
(ii) Reaction of 1 with C0 .................................. 21
(2) Preparation of (n 1-TMPP)Mo(C0)5 (3) .............. 21
(3) Preparation of (TMPP)W(CO)3 (4) ...................... 22
(4) Preparation of (TMPP)W(CO)4 (5) ...................... 22
(5) Preparation of (TMPP)W(CO)5 (6) ...................... 22
(6) Preparation of (T MPP)Cr(C0)3 (7) ..................... 23
(7) Preparation of (TMPP)Cr(CO)4 (8) ..................... 23
(8) Preparation of (TMPP)Cr(CO)5 (9) ..................... 24
(9) Reactions of (TMPP)M(C0)3 (M = M0, 1; W, 4)
with Me02CC_=_CC02Me .................................... 24
(i) Preparation of
(TMPP)Mo(CO)3(Me02CCECC02Me) (10) ..... 24
(ii) Preparation of
(T MPP)W(C0)3(Me02CCECC02Me) (11) ....... 24
(10) Reactions of (T MPP)Mo(C0)3 with C02 .......... 25
(i) Without NaPF6 .............................................. 25
(ii) With NaPF6 or KBF4 ................................... 25
(11) Reaction of (T MPP)W(C0) 3 with C02 ............. 26
(12) Reactions of (T MPP)M(C0)3 with 02
(M = M0, 1; W, 4) ............................................. 26
(13) Reactions of (T MPP)M(C0)3 with 802 ............ 27
(i) Solution Reactions ....................................... 27
(ii) Solid State Reactions .................................. 27
(iii) NMR Solution Reactions ........................... 28
C. X-ray Crystallographic Studies ...................................... 28
(1) (nZ-TMPP)Mo(C0)4 (2). ..................................... 28
(2) (T MPP)Mo(C0)5 (3) ........................................... 31
(3) (TMPP)Cr(C0)3-CH2C12 (7)oCH2Cl2 ................. 32
(4) (TMPP)Cr(CO)4 (8) ............................................. 32
3. Results and Discussion ........................................................... 33
A. Synthses of (n 3-TMPP)M(C0)3 (M = W, 4; Cr, 7) ....... 33

viii

B. Carbonylation Reactions of (TMPP)M(C0)3 (M = M0,

1; W, 4; Cr, 7) ................................................................ 35
(1) Syntheses ............................................................. 35
(2) NMR Studies of 2-9 ............................................. 38
(3) Molecular Structures of 2, 3, 7 and 8 .................. 51
C. Reactions of (T MPP)M(C0)3 with
Substituted Acetylenes ( M = Mo, 1; W, 4) ................... 61
D. Oxygenation Reactions of (TMPP)M(C0)3
(M = M0, 1; W, 4) .......................................................... 65
E. Carbon Dioxide Reactions of (TMPP)M(C0)3
(M = M0, 1; W, 4) ......................................................... 68
F. Sulfur Dioxide Reactions of (T MPP)M(C0)3
(M=Mo,1;W,4) .......................................................... 70
G. Summary ........................................................................ 72
List of References .................................................................. 75

CHAPTER III. COORDINATION CHEMISTRY OF TRIS(2,4,6-
TRIMETHOXYPHENYL)PHOSPHINE WITH

LATE TRANSITION METALS ............................. 78
1. Introduction ............................................................................. 79
2. Experimental Section .............................................................. 80
A. Physical Measurements .................................................. 80
B. Synthesis ........................................................................ 81
(1) Preparation of CoH(TMPP-0)2 (12) .................... 82
(2) Preparation of [CoIH(TMPP-0)2][BF4] (13) ....... 82
(3) Preparation of NiH(TMPP-0)2 (14) ..................... 82
(4) Preparation of [Nim(TMPP-0)2][BF4] (15) ........ 83
(5) Preparation of [Pd(TMPP)2][BF4]2 (l6) .............. 83
(6) Preparation of Pd(TMPP-0)2 (17) ....................... 84
(7) Preparation of [Pt(NCCH3)2(TMPP)2][BF4]2
(18) ......................................................................... 84
(8) Preparation of Pt(TMPP-0)2 (l9) ........................ 85

1X

(i) Reactions of PtCl2(NCC6H5)2 with

2 equiv. of TMPP .............................................. 85
(ii) Reactions of [Pt(NCCH3)4][BF4]2
with 4 equiv. of TMPP ...................................... 85
(9) Preparation of PtCl(TMPP)(TMPP-0) (20) ......... 86
(10) Preparation of Cd(N03)2(TMPP) (21) ............... 86
(11) Preparation of CdCl2(TMPP)2 (22) ................... 87
(12) Preparation of [Cd(TMPP)2][BF4]2 (23) ........... 87
C. X-ray Crystallographic Studies ...................................... 88
(1) CoH(TMPP-0)2 (12) ............................................ 88
(2) [Nim(TMPP-0)2][BF4] (15) ................................ 89
(3) [Pd(TMPP)2][BF4]2 (16) ..................................... 89
(4) Pd(TMPP—0)2 (17) ............................................... 9O
(5) [Pt(NCCH3)2(TMPP)2][BF4]2 (18) ..................... 90
(6) PtCTMPP-0)2-3EtCN (19)-3EtCN ........................ 91
(7) Cd(N03)2(TMPP) (21) ......................................... 92
(8) [Cd(TMPP)2][BF4]2 (23) ..................................... 93
3. Results and Discussion ........................................................... 93
A. Reactions of CoII and TMPP ......................................... 93
(1) Syntheses .............................................................. 93
(2) Electrochemistry of 12 ........................................... 94
(3) NMR Studies of 12 and 13 ................................... 94
(4) Molecular Structures of 12 ................................... 94
B. Reactions of NiII and TMPP .......................................... 95
(1) Syntheses .............................................................. 95
(2) Electrochemistry of 14 ........................................... 96
(3) NMR Studies of 14 and 15 ................................... 96
(4) Molecular Structures of 14 and 15 ....................... 98
C. Reactions of PdII and TMPP .......................................... 98
(1) Syntheses .............................................................. 98
(2) NMR Studies of 16 and 17 ................................... 105
(3) Molecular Structures of 16 and 17 ....................... 107
(4) Reactions of 16 with Small Molecules ................ 113
D. Reactions of Pt11 and TMPP ........................................... 113
(1) Syntheses .............................................................. 113
(2) NMR Studies of 18, 19 and 20 ............................. 115

X

(3) Molecular Structures of 18 and 19 ....................... 123

E. Reactions of Cd11 and TMPP .......................................... 130

(1) Syntheses .............................................................. 130

(2) NMR Studies of 21-23 ......................................... 131

(3) Molecular Structures of 21 and 23 ....................... 133

4. Summary ........................................................................ 139
List of References ........................................................................ 140

CHAPTER IV. CHEMISTRY OF METAL HALIDE
COMPLEXES WITH A PHOSPHONIUM

HALIDE AND OTHER ORGANIC HALIDES ....... 145
1. Introduction ............................................................................. 146
2. Experimental Section .............................................................. 147
A. Physical Measurements .................................................. 147
B. Synthesis ........................................................................ 147
(1) Preparation of [H-TMPP]2[Fe2Cl6] (24) ............. 148
(2) Preparation of [PPh4]2[Fe2Cl6] (25) .................... 148
(3) Preparation of [Et4N]2[Fe2C16] (26) .................... 149
(4) Preparation of [ppn]2[Fe2Cl6] (27) ...................... 149
(5) Preparation of [AsPh4]2[Fe2Cl6] (28) .................. 149
(6) Preparation of [BzNEt3]2[Fe2C16] (29) ............... 150
(7) Reactions of FeCl2 and Me3NHCl ....................... 150
(8) Reactions of FeCl2 and NH4C1 ............................ 150
(9) Preparation of [PPh4]2[Fe2(u-0)Cl6] (31) .......... 151
(10) Preparation of [Et4N]2[Fe2(u-0)C16] (32) ........ 151
(11) Reactions of A2[Fe2Cl6] with Nitrogen
Donors (A = PPh4 and Et4N) ............................. 152
(i) Preparation of Fe2Cl4(2,2'-bpym)3 (34)) ..... 152
(a) Reaction of [PPh4]2[Fe2Cl(,] with 2,2'-
bpym ........................................................... 152
(b) Reaction of FeCl2 with 2,2'-bpym ........... 152
(ii) Preparation of [Et4N]Cl-Fe2Cl4(Me0H)4(u-
2,2'-bpym) (35)

Reaction of [Et4N]2[Fe2C16] with 2,2'-bpym 152

xi

(iii) Preparation of FeCl2(2,2'-bpy) (36)
Reactions of A2[Fe2Cl6] with 2,2'-bpy

(A = PPh4 and Et4N) ........................................ 153
(iv) Reactions of A2[Fe2Cl6] with 4,4'-bpy
(A = PPh4 and Et4N) ........................................ 153
(12) Preparation of Fe4C13(THF)6 (33) ..................... 154
(13) Reactions of Fe4C13 (T HF)6 with
Nitrogen Donors ................................................ 154
(i) Reactions of Fe4C13(THF)6 with one
equiv. of 2,2-bpym ........................................... 154
(ii) Reactions of Fe4Clg(THF)6 with two
equiv. of 2,2-bpym ........................................... 155
(iii) Reactions of Fe4Cl3(THF)6 with two
equiv. of 2,2-bpy .............................................. 155
(iv) Reactions of Fe4Clg(THF)6 with an
excess of 4,4'-bpy .............................................. 156
(14) Preparation of [Mn(2,2'-bpym)2][BF4]2 (37) ..... 156
(15) Reactions of Fe4Clg(THF)6 with
[Mn(2,2'-bpym)2][BF4]2 .................................... 157
(16) Preparation of Mn4Clg(THF)6 (38) ...................... 157
(17) Preparation of [H-TMPP]2[C02C16] (39) ........... 157
(18) Preparation of [H-TMPP]2[Mn2Cl6] (40) .......... 158
C. X-ray Crystallographic Studies ...................................... 159
(1) [PPh4]2[Fe2Cl6] (25) ............................................ 159
(2) [Et4N]2[Fe2Cl6] (26) ............................................ 160
(3) [ppn]2[Fe2Cl6] (27) .............................................. 160
(4) [AsPh4]2[Fe2Cl6] (28) ......................................... 161
(5) [BzNEt3]2[FeCl4] (30) ......................................... 162
(6) Fe4Clg(THF)6 (33) ............................................... 163
(7) Fe2Cl4(2,2'-bpym)3 (34) ...................................... 163
(8) [Et4N]Cl-[Fe2Cl4(Me0H)4(u-2,2'-bpym)] (35) 164
(9) FeCl2(2,2'-bpy) (36) ............................................. 164
(10) [Mn(H20)2(2,2'-bpym)2][BF4]2-2(H20) ........... 165
(11) [H-TMPP]2[C02C16] (39) ................................... 166
3. Results and Discussion ........................................................... 167
A. Chemistry of [Fe2C16]2' and [Fe2(u-0)Cl6]2" .............. 167
(1) Syntheses .............................................................. 167
(2) Molecular Structures of 25-28 and 30 .................. 167

Xll

(3) Magnetic Studies of 24—28 ................................... 185
(4) Reactions of A2[Fe2Cl6] with 02 (A =

PPh4 (25), Et4N (26))
Preparation of A2[Fe2(u-0)Cl6] (A =
PPh4 (31), Et4N (32)) .......................................... 199
B. Reactions of A2[Fe2Cl6] with Nitrogen Donors
(A = PPh4 (25), Et4N (26)) ............................................. 201
C. Chemistry of Fe4Clg(THF)6 (33) ................................... 209
(1) Synthesis and Molecular Structure of 33 ............. 209
(2) Magnetic Properties of 33 .................................... 213
(3) Reactions with Nitrogen Donors .......................... 220
D. Chemistry of [Mn(2,2'-bpym)2][BF4]2 (37) .................. 224
(1) Synthesis .............................................................. 224
(2) Molecular Structure of
[Mn(H2O)2(2,2'-bpym)2] [BF4]2-2(H2O) ............. 224
(3) Magnetic Properties of 37 .................................... 228
(4) Reaction with Fe4C13(THF)6 ............................... 228
E. Chemistry of [H-TMPP]2[M2C16]
(M = C0 (39), Mn (40)) ................................................. 232
(1) Synthesis .............................................................. 232
(2) Molecular Structure of 39 .................................... 232
(3) Magnetic Properties of 39 .................................... 237
F. Synthesis of Mn4ClgCTHF)6 ........................................... 237
4. Summary ................................................................................. 240
List of References ........................................................................ 241

APPENDIX. TABLES OF ATOMIC POSITION AL
PARAMETERS AND EQUIVALENT
ISOTROPIC DISPLACEMENT PARAMETERS ..... 245

xiii

1.1.

2.1.

2.2.

2.3.
2.4.
2.5.
2.6.

2.7.

2.8.

2.9.

3.1.

3.2.

LIST OF TABLES

pKa values for methoxy substituted triphenylphosphines

(from reference 6d) ....................................................................

Summary of crystallographic data for (TMPP)Mo(C0)4 (2)

and (T MPP)Mo(CO)5 (3) ..........................................................

Summary of crystallographic data for (T MPP)Cr(C0)3 (7),

(TMPP)Cr(CO)4 (8) ...................................................................

N MR spectroscopic data for compounds 1-3 ...........................
NMR spectroscopic data for compounds 4-6 ...........................
NMR spectroscopic data for compounds 7-9 ...........................

Selected bond distances (A) and bond angles (°)

for (TMPP)Mo(CO)4 (2) ............................................................

Selected bond distances (A) and bond angles (°)

for (TMPP)Mo(CO)5 (3) ............................................................

Selected bond distances (A) and bond angles (°)

for (T MPP)Cr(C0)3-CH2C12 (7)-CH2C12 .................................

Selected bond distances (A) and bond angles (°)

for (TMPP)Cr(CO)4 (8) .............................................................

Summary of crystallographic data for
[Ni(TMPP-0)2][BF4]-2(CH3)2C0 (lS-2(CH3)2C0) ..............

Selected bond distances (A) and bond angles (deg)
for [Ni(TMPP—0)2][BF4].2(CH3)2C0 (15-2(CH3)2C0) .........

xiv

page
5

29

30

40
41

42

53

55

57

59

99

101

3.3.

3 .4.

3.5.

3.6.

3.7.

3.8.

3.9.

4.1.

4.2.

4.3.

4.4.

4.5.

4.6.

Summary of crystallographic data for [Pd(TMPP)2][BF4]2
(16) and Pd(TMPP—0)2-nCH2Cl2 (17-nCH2Cl2) ....................... 109

Selected bond distances (A) and bond angles (°)
for [Pd(TMPP)2][BF4]2 (16) ..................................................... 111

Summary of crystallographic data for
[Pt(NCCH3)2(TMPP)2][BF4]2 (18) and Pt(TMPP-0)2o3EtCN

(193EtCN) ................................................................................ 124
Selected bond distances (A) and bond angles (°) for
[Pt(NCCH3)2(TMPP)2][BF4]2 (18) ........................................... 127
Selected bond distances (A) and bond angles (°) for
Pt(TMPP-0)2-3EtCN (19-3EtCN) ............................................ 129
Summary of crystallographic data for Cd(TMPP)(N03)2 (21)

and [Cd(TMPP)2][BF4]2 (23) .................................................... 134
Selected bond distances (A) and bond angles (°) for
Cd(TMPP)(N03)2 (21) .............................................................. 136
Summary of crystallographic data for A2[Fe2Cl6]

(A = PPh4, 25; Et4N, 26; ppn, 27; AsPh4, 28) ........................... 168
Selected bond distances (A) and bond angles (°) for
[PPh4]2[Fe2C16] (25) ................................................................. 170
Selected bond distances (A) and bond angles (°) for
[Et4N]2[Fe2C15] (26) ................................................................. 172
Selected bond distances (A) and bond angles (°) for

[ppn]2[Fe2Cl6] (27) ................................................................... 174
Selected bond distances (A) and bond angles (°) for
[AsPh4]2[Fe2C16] (28) ............................................................... 176

Summary of crystallographic data for
[BzNEt3]2[FeCl4] (30) .............................................................. 182

XV

4.7. Selected bond distances (A) and bond angles (°) for

4.8.

4.9.

4.10.

4.11.

4.12.

4.13.

4.14.

4.15.

4.16.

A.l.

A.2.

xvi

[BzNEt3]2[FeCl4] (30) .............................................................. 184
Summary of crystallographic data and maximum magnetic

moments for the series of A2[Fe2Cl6] (A = H-TMPP, 24;
PPh4, 25; Et4N, 26; ppn, 27; AsPh4, 28) ................................... 200
Summary of crystallographic data for Fe2Cl4(2,2'bpym)3 (34),
[Et4NJC1°F62C14(M60H)4(u-2,2'-bpym) (35),
and FeCl2(2,2'-bpy) (36) ........................................................... 202
Selected bond distances (A) and bond angles (°) for
Fe2Cl4(2,2'-bpym)3 (34) ........................................................... 204
Summary of crystallographic data for Fe4C13(THF)6 (33) ..... 214
Selected bond distances (A) and bond angles (°) for

Fe4C13(THF)6 (33) ................................................................... 216
Summary of crystallographic data for
[Mn(2,2'-bpym)2(H20)2][BF4]2-2(H20) ........................ 225
Selected bond distances (A) and bond angles (°) for
[Mn(2,2'-bpym)2(H20)2] [BF4]2o2(H20) ......................... 227
Summary of crystallographic data for

[H-TMPP]2[Co2Cl6] (39) ......................................................... 233
Selected bond distances (A) and bond angles (°) for
[H-TMPP]2[C02C16] (39) ......................................................... 235
Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for (TMPP)Mo(C0)4 (2) ........................................ 246
Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for (TMPP)Mo(CO)5 (3) ........................................ 249

A.3. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for (TMPP)Cr(C0)3-CH2C12 (7 -CH2C12) .............. 251

A.4. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for (TMPP)Cr(CO)4 (8) .......................................... 254

A5. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [NiCTMPP-0)2][BF4]-2(CH3)2C0
(15-2(CH3)2CO) ...................................................................... 257

A6. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [Pd(TMPP)2][BF4]2 (16) ................................... 262

A7. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [Pt(NCCH3)2(TMPP)2][BF4]2 (18) ................... 266

A8. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for Pt(TMPP-0)2-3EtCN (19-3EtCN) ..................... 271

A9. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for Cd(N03)2(TMPP) (21) ..................................... 276

A.10. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [PPh4]2[Fe2Cl6] (25) ....................................... 279

All. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [Et4N]2[Fe2Cl6] (26) ....................................... 281

A.12. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [ppn]2[Fe2Cl6] (27) ....................................... 282

xvii

A.13. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [AsPh4]2[Fe2Cl6] (28) ..................................... 286

A.14. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [BzNEt3]2[FeCl4] (30) ..................................... 288

A.15. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for Fe4C13(THF)6 (33) .......................................... 291

A.16. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for Fe2Cl4(2,2'-bpym)3 (34) .................................. 293

A.17. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for FeCl2(2,2'-bpy) (36) ........................................ 294

A.18. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [Mn(2,2'-bpym)2(H20)2][BF4]2-2(H2O) ......... 295

A.19. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard
deviations for [H-TMPP]2[Co2C15] (39) ................................ 296

xviii

LIST OF FIGURES

page

1.1. Plot of the cone angle vs the v(C0)A1 stretching vibration for

various Ni(C0)3(PR3) complexes ............................................. 7
2.1. Variable-temperature 1H N MR spectra of (TMPP)Mo(C0)4 (2)

in acetone-d6 ............................................................................. 43
2.2. Variable temperature 1H NMR spectra of (T MPP)W(C0)3 (4)

in acetone-d6 ............................................................................. 44
2.3. Variable temperature 1H NMR spectra of (T MPP)W(C0)4 (5)

in acetone—d6 ............................................................................ 45
2.4. Variable temperature 1H N MR spectra of (TMPP)Cr(C0)3 (7)

in acetone-d6 ............................................................................. 46
2.5. Variable temperature 1H NMR spectra of (TMPP)Cr(CO)4 (8)

in acetone-d6 ............................................................................. 47
2.6. Variable-temperature 1H NMR spectra of (T MPP)Mo(C0)5 (3)

in acetone—ds ............................................................................. 49
2.7. ORTEP drawing of (TMPP)Mo(CO)4 (2) ................................. 52
2.8. ORTEP drawing of (TMPP)Mo(CO)5 (3) ................................. 54
2.9. ORTEP drawing of (TMPP)Cr(CO)3 (7) .................................. 56
2.10. ORTEP drawing of (T MPP)C1'(CO)4 (8) .................................. 58
2.11. 1H NMR spectrum of

(TMPP)Mo(CO)3(Me02CCECC02Me) .................................. 62

xix

2.12.

3.1.

3.2.
3.3.

3.4.

3.5.

3.6.
3.7.

3.8.

3.9.

3.10.

3.11.
3.12.
3.13.

3.14.

3.15.

Solution IR spectra of (TMPP)Mo(CO)3 and 02 at various
reaction times ............................................................................ 67

Variable temperature 1H NMR spectra of Ni(TMPP-0)2 (14)

in acetone-d6 ............................................................................ 97
ORTEP drawing of [Ni(TMPP—0)2][BF4] (15) ......................... 100
Cyclic voltammogram of [Pd(TMPP)2][BF4]2 (16) in
0.1 M solution of TBAPF6 in CH2C12 ........................................ 103
Variable temperature 1H NMR spectra of [Pd(TMPP)2][BF4]2
(16) in acetone-d6 ...................................................................... 104
Room temperature 1H NMR spectrum of Pd(TMPP—0)2 (17)
in chloroform-d1 ....................................................................... 106
ORTEP drawing of [Pd(TMPP)2][BF4]2 (16) ........................... 110
PLUTO drawing of Pd(TMPP—0)2 (17) .................................... 112
Room temperature 1H NMR spectrum of [Pt(NCCH3)2-
(TMPP)2][BF4]2 (18) in acetonitrile-d3 .................................... 116
Room temperature 1H NMR spectrum of Pt(TMPP-0)2 (19)
in acetonitrile-d3 ....................................................................... 118

Room temperature 1H NMR spectrum of

PtCl(TMPP)(TMPP—0) (20) in acetonitrile-d3 ........................ 119
31P NMR spectrum of PtC1(T MPP)(T MPP-O) (20) ................ 120
Proposed structure for PtCl(TMPP)(TMPP—0) (20) ................ 121
ORTEP drawing of [Pt(NCCH3)2(TMPP)2][BF4]2 (18) ......... 125
Space filling diagram of

[Pt(NCCH3)2(TMPP)2] [BF4]2 (18) .......................................... 126
ORTEP drawing of PtCTMPP—0)2 (l9) .................................... 128

XX

3.16. 1H NMR spectrum of Cd(N03)2(TMPP) (21) in acetone-d6 132

3.17. ORTEP drawing of Cd(N03)2(TMPP) (21) ............................. 135
3.18. PLUTO drawing of [Cd(TMPP)2][BF4]2 (23) ......................... 137
4.1. ORTEP drawing of [PPh4]2[Fe2Cl6] (25) ................................. 169
4.2. ORTEP drawing of [Et4N]2[Fe2C16] (26) ................................. 171
4.3. ORTEP drawing of [ppn]2[Fe2C16] (27) ................................... 173
4.4. ORTEP drawing of [AsPh4]2[Fe2Cl6] (28) ............................... 175

4.5. Packing diagram of [PPh4]2[Fe2C16] (25) viewed along the
b direction .................................................................................. 178

4.6. Packing diagram of [Et4N]2[Fe2Cl6] (26) viewed along the
c direction .................................................................................. 179

4.7. Packing diagram of [ppn]2[Fe2C16] (27) viewed down the

b direction .................................................................................. 180
4.8. Packing diagram of [AsPh4]2[Fe2Cl6] (28) viewed along the

b direction .................................................................................. 181
4.9. ORTEP drawing of [BzNEt3]2[FeCl4] (30) .............................. 183

4.10. Plots of (a) )(m and me vs the absolute temperature and (b)

the effective moment vs the absolute temperature at 5T for
[ll-TMPP]2[Fe2Cl6] (24) ......................................................... 186

4.11. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced
magnetization vs the magnetic field for
[H-TMPP]2[Fe2Cl6] (24) ........................................................ 187

4.12. Plots of (a) )(m and XmT vs the absolute temperature and (b)
the effective moment vs the absolute temperature at 5T for

[PPh4]2[Fe2Cl6] (25) ............................................................... 190

xxi

4.13. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HH) and (b) reduced
magnetization vs the magnetic field for

[PPh4]2[Fe2Cl6] (25) ............................................................... 191

4.14. Plots of (a) )(m and me vs the absolute temperature and (b)
the effective moment vs the absolute temperature at 5T for

[ppn]2[Fe2Cl6] (27) ................................................................. 192

4.15. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced
magnetization vs the magnetic field for

[ppn]2[Fe2C16] (27) .................................................................. 193

4.16. Plots of (a) xm and XmT vs the absolute temperature and (b)

the effective moment vs the absolute temperature at 5T for
[Et4N]2[Fe2Cl6] (26) .............................................................. 195

4.17. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (Hfl') and (b) reduced
magnetization vs the magnetic field for

[Et4N]2[FezCl6] ....................................................................... 1 96

4.18. Plots of (a) )(m and )(mT vs the absolute temperature and (b)

the effective moment vs the absolute temperature at 5T for
[AsPh4]2[Fe2C15] (28) ............................................................. 197

4.19. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced
magnetization vs the magnetic field for

[AsPh4]2[Fe2C16] (28) ............................................................. 198
4.20. ORTEP drawing of Fe2C14(2,2'-bpym)3 (34) ........................... 203

4.21. Packing diagram of Fe2C14(2,2'-bpym)3 (34) viewed down
the b axis ................................................................................... 206

4.22. Packing diagram of Fe2C14(2,2'-bpym)3 (34) viewed along
the c direction ........................................................................... 207

xxii

4.23.

4.24.

Plots of (a) Xm and me vs the absolute temperature and (b)

the effective moment vs the absolute temperature for
F€2Cl4(2,2'-bpym)3 (34) .......................................................... 208

Plot of xm vs the absolute temperature for
Fe2C14(2,2'-bpym)3 (34) obtained from the experimental data
and by fitting to the Heisenberg-Dirac-Van Vleck equation

(assume D << J) ........................................................................ 210
4.25. Packing diagram of [Et4N]Cl-[Fe2Cl4(MeOH)4(l.l-2,2'-bpym)]

(35) ............................................................................................ 212
4.26. ORTEP drawing of Fe4C13(THF)6 (33) ................................... 215

4.27.

4.28.

4.29.

4.30.

4.31.

4.32.

Structures of [Fe2Cl6]2' (top) and Fe4C13(THF)6 (bottom)

can be extracted as fragments (circled with dash line) from

the layer structure of FeC12 with 0 as Fe, 0 as Cl,

and O asTHF ........................................................................... 217

Plots of (a) neff vs T, (b) reduced magnetization vs the ratio
of magnetic field over the absolute temperature (Hfl‘) and
(c) reduced magnetization vs the magnetic field for

Fe4C13(THF)6 (33) ................................................................... 218

Plots of (a) Xg vs the absolute temperature and (b)ng vs the
absolute temperature for the product obtained from the

reaction of Fe4C13(THF)6 with 2,2'-bpy .................................. 222
Plots of (a) Xg vs the absolute temperature and (b)ng vs the
absolute temperature for the product obtained from the

reaction of Fe4C13(THF)6 with 2,2'-bpym ............................... 223
ORTEP drawing of the cation [Mn(2,2'—bpym)2(H20)2]2+ ..... 226

Plots of (a) )(m and IIXm vs the absolute temperature, and
(b) the effective magnetic moment vs the absolute
temperature for [Mn(2,2'-bpym)2][BF4]2 (37) ........................ 229

xxiii

 

4.33. Plots of (a) Xg vs the absolute temperature and (b) ng vs the
absolute temperature for the product obtained from the
reaction of Fe4C18(THF)6 with [Mn(2,2'-bpym)2]-
[BF4]2 ...................................................................................... 231

4.34. ORTEP drawing of [H-TMPP]2[Co2Cl6] (39) ......................... 234

4.35. Packing diagram of [H-TMPP]2[C02C16] (39) viewed down
the b direction ........................................................................... 236

4.36. Plots of (a) Xm and XmT vs the absolute temperature and (b)
the effective moment vs the absolute temperature for
[H-TMPP]2[C02CI6] (39) ......................................................... 238

4.37. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced
magnetization vs the magnetic field for
[H-TMPP]2[C02C16] (39) .................... 239

xxiv

 

(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)

 

 

 

 

 

 

 

 

 

(9)

(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)

 

 

 

 

 

 

 

 

 

 

 

 

LIST OF COMPOUNDS

(TMPP)Mo(CO)3
(TMPP)Mo(C0)4
(TMPP)Mo(CO)5
(TMPP)W(CO) 3
(TMPP)W(CO)4
(TMPP)W(CO) 5
(TMPP)Cr(C0)3
(TMPP)Cr(CO)4
(TMPP)Cr(CO) 5
(TMPP)Mo(C0)3(Me02CCECC02Me)
(TMPP)W(CO)3(Me02CCECC02Me)
C011(TMPP-0)2

[CoIH(TMPP- 0) 2] [B F4]

N i11(TMPP- 0)2

[Ni111(TMPP- 0)2] [BF4]
[PdH(TMPP)2] [BF4]2
PdII(TMPP- 0)2

[PtH(NCCH 3)2(TMPP)2] [BF4]2
PtH(TMPP-0)2
PtClCTMPP)(TMPP— 0)
Cd(N03)2(TMPP)
CdCl2(TMPP)2

XXV

(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
(33)
(34)
(35)
(36)
(37)
(38)
(39)
(40)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

[CdH(TMPP)2][BF4]2
[H-TMPP]2[Fe2Cl6]
[PPh412lFezC16]
[EleleezClcl
[ppnlleezClts]

[AsPh412lFezC16]
[BzNEt3]2[Fe2Cl6]

[BzNEt3]2[FeCl4]
[PPh4]2[F€2(11'0)C161
[Et4N]2[Fez(u-O)C16]
Fe4C13(THF)6
F62C14(2.2'-bpym)3
[Et4N1Cl-[F62C14(M60H)4(u-2,2'-bpym)]
FeCl2(2,2'-bpy)
[Mn(2,2'-bpym)2][BF4]2
Mn4C18(THF)6
[H-TMPP]2[C02C16]
[H-TMPPllen2C16]

xxvi

O

A
Ag/AgCl
br

f3
CH3-TMPP

cm'1
° C
Xm
Xg

d

D

6

LIST OF SYMBOLS AND ABBREVIATIONS

Angstrdm
silver/silver chloride reference electrode
broad
Bohr magneton
tris(2,4,6-trimethoxyphenyl)methyl phosphonium
wavenumber
degree centigrade
molar magnetic susceptibility
gram magnetic susceptibility
doublet (NMR), day, deuterated
zero-field splitting
parts per million (ppm)
anodic peak potential
cathodic peak potential
electron paramagnetic resonance
electron magnetic unit
molar extinction coefficient
wavelength
gram, epr g tensors
gauss
hour
field
ratio of field over temperature
tris(2,4,6-trimethoxyphenyl)protic phosphonium
infrared
coupling constant (NMR), exchange coupling constant
Boltzmann constant
Kelvin
megaHertz
mole per liter
xxvii

min
mL
mmol

lieff
11B
M/NB

nm
NMR

PPh3
ppm
red
r.t.

sh
SQUID
TBAPF6
IBu

TMPP
TMPP-0
TMS

UV

VS

><€

methyl

medium, multiplet

minute

milliliter

millimole

bridging ligand

effective magnetic moment

Bohr magneton

reduced magnetization

Avogadro constant

nanometer

nuclear magnetic resonance

frequency

oxidation

tricyclohexylphosphine
triphenylphosphine

parts per million

reduction

room temperature

singlet (NMR), strong

shoulder

Superconducting Quantum Interference Device
tetra-n-butylammonium hexafluorophosphate
tertiary—butyl

temperature, Tesla
tris(2,4,6-trimethoxyphenyl)phosphine
Pl{C6H2(OCH3)3}2{C6H2(OCH3)2O}]'
tetramethylsilane

ultraviolet

volt

versus, very strong

weak

halide

xxviii

CHAPTER I

INTRODUCTION

1. Transition Metal Complexes with Fuctionalized

Phosphines.

Bulk syntheses of organic compounds are catalyzed by a variety of
transition metal complexes under homogeneous conditions. Late transition
metal-phosphine complexes (e.g. Co, Rh) have been used in olefin
hydrogenation as well as hydroformylation, hydrosilation, polymerization
of olefins and acetylenes.1 It is known that ligand dissociation and
reassociation are the key steps in most catalytic cycles. Dissociation of an
ancillary ligand opens up an empty site for an incoming substrate, while
reassociation of this ligand restores the compound to its original active
form and simultaneously releases the desired products as observed in the
hydrogenation cycle of Wilkinson's catalyst (Rh(PPh3)3Cl) (PPh3 =
triphenylphosphine).2 In response to the requirement for a good, yet not
permanent, leaving group, researchers have developed a series of (P,0)
ligands that participate in a strong metal-phosphorus interaction and weak
metal-oxygen interaction(s) that are easily cleaved. By modifying the
substituents on the phosphine, one can vary both the electronic and steric
properties of the ligand, which in turn affects the reactivity and
stereoselectivity of the desired product. It has been found that transition
metal complexes with (P,0) ligands exhibit an unusual selectivity effect in
catalysis, the details of which are discussed in the following sections.3
2. Tris(2,4,6-trimethoxyphenyl)phosphine (TMPP).

The molecule tris(2,4,6-trimethoxyphenyl)phosphine (T MPP) was
first prepared by Protopopov et at. from the reaction of PC13 and 1,3,5-
tn'methoxybenzene in the presence of ZnC12.4a'b The phosphine was later
prepared again by Wada et al., by an alternate route that involves lithiation

of 1,3,5-trimethoxybenzene, followed by coupling with tripheny-

3

phosphite.49'd This procedure was further modified and used in our
laboratories (Scheme 1.1).5 In spite of its synthesis being known for over
thirty years, the X-ray structure was not determined until recently in our
laboratories.521

The physical and chemical properties of TMPP have been studied by
Wada and co-workers, who reported a high basicity (pKa = 11.2) and a
large cone angle of ~ 184°."tC-d Wada further investigated the use of the
highly basic TMPP in organic transformations as well as in the extraction
of metal ions such as Fe3+ and Ga3“.6 The high basicity of TMPP was
explained by the presence of the ortho-methoxy substituents. It can be
clearly seen in Table 1.1 that the basicity of phenylphosphines increases
mainly with increasing the number of methoxy substituents, while the
basicity is only slightly affected by the positions of the substituents. This is
supported by the pKa values of (ortho-OMeC6H4)3P (pKa = 4.47) vs (para-
0MeC6H4)3P (pKa = 4.75), (ortho-OMeC6H4)2PPh (pKa = 4.01) vs (para-
0MeC6H4)2PPh (pKa = 4.06), and (0rth0—0MeC6I-I4)PPh2 (pKa = 3.33) vs
(para-0MeC6H4)PPh2 (pKa = 3.67), as shown in Table 1.1.6 The basicity
of TMPP was further examined in our laboratories by measuring the A1
mode of the carbonyl stretching vibration of the complex Ni(C0)3(TMPP).
The complex was prepared in situ by the method described by Tolman who
reported the electron donating properties of tertiary phosphines by
measuring the IR spectra for a wide variety of Ni(C0)3(PR3)
compounds.721 The v(C0) A1 vibration of the TMPP complex appeared at
1963 cm'l, which is lower than that reported by Tolman for P"Bu3 which
occurs at 2056 cm'l. This result is compatible with the data reported by
Wada and co—workers who used pKa values as an indication of the basicity

of TMPP. A plot of the cone angle versus the v(C0) A1 vibration

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for various Ni(C0)3(PR3) complexes is presented in Figure 1.1.7,5b

In addition to influencing the electronic properties of the phosphorus
lone pair, the methoxy substituents also play an important role in the
stereochemistry of TMPP. The cone angle of TMPP is similar to that of
tris(perflurophenyl)phosphine but smaller than that of trimesitylphosphine
and tri-o-tolyl phosphine.8 Bulky phosphines such as tricyclohexyl, tri-
tert-butylphosphine, tri-o-tolyl phosphine, and trimesitylphosphine are
known to stabilize transition metal complexes with low coordination
numbers, which lead to highly reactive metal centers. Kubas et al.
discovered and structurally characterized the first dihydrogen metal
complexes, M(C0)3(PR3)2(H2) (M = Cr, Mo, W, R = iPr, Cy) from the
reaction of unsaturated metal carbonyls supported by two bulky phosphines
with H2.9 Bulky phosphines have also been used to isolate a series of two-
coordinate complexes of Pt(0) and Pd(0).10 Due to the presence of two
ortho methoxy groups on each phenyl ring, TMPP is able to bind to a
metal center in monodentate, bidentate, or tridentate modes through the
phosphorus atom and/or one or two oxygen atoms, as depicted in Scheme
1.2. It is reasonable to expect that this flexibility in binding will facilitate
interesting reactions that differ from the traditional bulky phosphine
chemistry.
3. Chemistry of TMPP with Transition Metal Complexes.

A. Group VI Metal Carbonyls.

Transition metal fixation and activation of small molecules such as
C02, N2, H2, 802, C0, and 02 are topics of considerable interest in areas
as diverse as biochemistry, catalysis, and pollution control.9,11'18 Due to
the instability of metal adducts of these molecules as well as the complexity

of their reactions, researchers have sought to prepare model compounds

 

 

.TMPP B ,
180°- ' 03P -(MeaSi)aP
c O
< 160 -
0
0 140° - .MethP
EtaP .
o _ 0 MeZPhP
120 M6313 0
1 [ .1(M80)3P
2050 2000 2070 2080 tom")

VA1(CO) IOI' LNI(CO)3

Figure 1.1. Plot of the cone angle vs the v(C0)A1 stretching vibration
for various Ni(C0)3(PR3) complexes.

R
R 5
monodentate 1:1) \ p/ R
1
n |
M
OMe
R, 0M6
R\'—.
bidentate {:1} 1|)
1
'1 M——0\
Me
MeO 0M6
MeO / \ _ OMe
tridentate :9 \ P
l
11 0 i ...0
\ ---- \
Me/ M Me
MeO 0Me

OMe

Scheme 1.2. Three commonly encountered bonding modes for TMPP.

9

involving bound forms of small molecules in order to better understand the
chemistry involved. Two main strategies have been applied to the fixation
of C02; these are (a) the use of highly basic transition metals and (b) the
combined use of an acidic metal (alkali metal ion) and a basic, low-valent
late transition metal.12 The use of highly basic transition metals such as
Ni, Ir, and Rh have successfully resulted in the isolation of a series of C02
transition metal adducts with C02 in various bonding modes (r11, r12).
Floriani and co-workers managed to trap the entire C02 molecule in an n3
mode with the use of acid-base bimetallic system.

Ether-phosphine metal complexes have been used in our research
group and in others to explore the reversible coordination of ether groups
in the presence of carbon monoxide. For example, reactions of CO with
group VI ether-phosphine metal carbonyls are reversible with one type of
ether-phosphine as reported by Lindner and co-workers, but irreversible
reaction with another type of ether-phosphine reported by Verkade and co-
workers, as depicted in Scheme 1.3. Work in our laboratories has centered
on the syntheses of series of fluxional TMPP metal compounds, inspired by
the arm-open/arm-close mechanism observed in functionalized
phosphines,11t16‘17 for the investigation of unusual reaction products with
small molecules that may be kinetically stabilized by the presence of a
bulky multidentate ligand. This work began with the syntheses of a series
of fluxional metal carbonyls (n3-TMPP)M(C0)3 (M = Cr, Mo, W), from
which the tetra- ((nZ-TMPP)M(C0)4) and penta-carbonyl derivatives ((111-
TMPP)M(C0)5) were obtained by reactions with C0. The M0 series, 01"—
TMPP)Mo(C0)y (x = 3, y = 3; x = 2, y = 4, x = 1, y = 5), constitutes the
first such fully characterized series of carbonyl complexes stabilized by a
single ancillaryligand. Details of the syntheses, structures and

10

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11

interconversions of the members of this series as well as the reactions of
(n3-TMPP)M(C0)3 with C02, N2, H2, 802, and 02 are discussed in
chapter 2.

B. Late Transition Metal Complexes.

In addition to the preparation of group VI carbonyl complexes, the
syntheses, characterization and properties of late transition metal
complexes with TMPP are presented in chapter 3. This research was
prompted by the well-established fact that weak metal—ether interactions
induce increased reactivity at the metal center. Examples of this effect are
observed selectivity enhancements in the Ni(II) catalyzed oligomerization
of ethane,321 the carbonylation and hydrocarbonylation catalyzed by
Co(II)3°‘d and Rh(I)3C, and the hydrogenation catalyzed by Pd(II)19, all of
which involve ether-phosphine ligands.

Homoleptic phosphino-phenoxide transition metal complexes were
reported long ago by Shaw et al. to occur by O-metallation of the oxygen
atom with dealkylation.20 As shown in Scheme 1.4, the phosphine ligand
undergoes dealkylation to form a metallacycle under conditions wherein
PtX2(PPh2(2-methoxypheny1))2 (X = Cl, 1) is refluxed with an alkyl halide
being produced as a by-product. A similar strategy was applied to the
syntheses of bis-phosphino-phenoxide complexes of the type M(TMPP—0)2
(M = Pd, Pt) from reactions of MC12(NCC6H5)2 with TMPP. Homoleptic
TMPP and TMPP-0 (the monodemethylated form of tris(2,4,6-
trimethoxyphenyl)phosphine) complexes have also been synthesized
beginning with the fully solvated transition metal complexes of group VIII
and two equivalents of TMPP for [M(TMPP)2][BF4]2 and four equivalents
of TMPP for high yields of M(TMPP-0)2). Electrochemical studies of
three related bis-phosphino-phenoxide complexes M(TMPP—0)2 (M = Co,

12

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13

Ni, Pd) were performed and are discussed in light of typical trends for
these metal oxidation states. Solid state structural determination of
NiH(TMPP-0)2 and its oxidized product [Ni111(TMPP-0)2][BF4] by X-ray
crystallography revealed an interesting isomerization, from trans to cis in
going from Ni(II) to Ni(III).

Due to the difficulty in preparing the fully solvated complexes for
Cd(II), TMPP complexes of Cd(II) were synthesized from the reactions of
a Cd(II) nitrate complex with TMPP to yield nitrate containing and nitrate
free products depending on the presence or absence of a nitrate abstraction
reagent. Details of these reactions are discussed in chapter 3.

C. Metal Halide Complexes.

The syntheses and magnetic studies of a series of dinuclear
complexes containing the ferrous chloride unit [Fe2C15P‘ with a variety of
cations are discussed in chapter 4. These investigations were prompted by
our discovery of the interesting ferromagnetic compound [H-
TMPP]2[Fe2Cl(,] that was unexpectedly isolated from the reaction of FeCl3
with TMPP.5b In related studies, the tetranuclear ferrous cluster
Fe4C13(THF)6 as well as two related dinuclear compounds [H-
TMPP]2[M2C16] (M = Mn, Co) are discussed. Reactions of this diferrous
compounds with polydentate aromatic nitrogen donors were performed and
the results are presented in light of the potential for the formation of

extended structures with ferri- or ferromagnetic properties.

14

List of References

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Tolman, C. A. Chem. Rev. 1977, 77, 313.

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Bader, A.; Lindner, E. Coord Chem. Rev. 1991, 108, 27 and
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13.

14.

15.

16.

17.

16

Chem. 197 9, I8, 3469. (t) Gambarotta, S.; Arena, F.; Floriani, C.;
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therein. (g) Gambarotta, 8.; Arena, F.; Floriani, C.; Zanazzi, P. F.
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Lee, G. R.; Maher, J. M.; Cooper, N. J. J. Am. Chem. Soc 1987,
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Nobile, C. F.; Latronico, M. Inorg. Chim. Acta 1992, 192, 183 and
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Organometallics 1992, II, 1450. (k) Fu, P.-F.; Khan, M. A.;
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T.; Nitta, S.; Yoshikawa, S.; Kobayashi, K.; Sakurai, T.; Yano, S.
Inorg. Chem. 1992, 31, 1058. (m) Ratliff, K. S.; Lentz, R. E.;
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therein. (n) Kitajima, N.; Hickichi, S.; Tanaka, M.; Moro-oka, Y. J.
Am. Chem. Soc. 1993, 115, 5496.

Kubiak, C. P.; Ratliff, K. S. Isr. J. Chem. 1991, 31, 3 and
references therein.

(a) Chatt, J.; Dilworth, J. R.; Richards, R. L. Chem. Rev. 197 8, 78,
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(a) Mingos, D. M. P. Transition Met. Chem. (London) 197 8, 3, 1.
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3003. (c) Ryan, R. R.; Kubas, G. J.; Moody, D. C.; Eller, P. G.
Struct. Bonding (Berlin) 1981, 46, 47 and references therein. ((1)
Moody, D. C.; Ryan, R. R. J. Chem. Soc. Chem. Commun. 1980,
1230. (e) Kubas, G. J.; Jarvinen, G. D.; Ryan, R. R. J. Am. Chem.
Soc. 1983, 105, 1883. (f) Toupadakis, A.; Kubas, G. J.; Burns, C.
J. Inorg. Chem. 1992, 31, 3810. (g)Godfrey, S. M.; McAuliffe, C.
A.; Ranger, G. C.; Kelly, D. G. J. Chem. Soc. Dalton Trans. 1993,
2809. (h) Ghatak, 1.; Mingos, M. P.; Hursthouse, M. B.; Abdul
Malik, K. M. Transition Met. Chem. 197 9, 4, 260.
(i)Schimme1pfennig, U.; Kalahne, R.; Schleinitz, K. D.; Wenschuh,
E. Z anorg. allg. Chem. 1991, 603, 21. (i) Heyke, 0.; Hiller, W.;
Lorenz, l.-P. Chem. Ber. 1991, 124, 2217. (k) Kubas, G. J. Acc.
Chem. Res. 1994, 27, 183.

(a) Lindner, E.; Mockel, H. A. M.; Kuhbauch, H.; Fawzi, R.;
Steimann, M. Inorg. Chem. 1993, 32, 1266.

(a) Mason, R.; Thomas, K. M.; Empsall, H. D.; Fletcher, S. R.; Heys,
P. N.; Hyde, E. M.; Jones, C. E.; Shaw, B, L. J. Chem. Soc., Chem.

18.

19.

20.

17

Commun. 1974, 612. (b) Jones, C. E.; Shaw, B. L.; Turtle, B. L. J.
Chem. Soc., Dalton Trans. 197 4, 922. (c) Empsall, H. D.; Heys, P.
N.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 197 8, 257. (d)
Rauchfuss, T. B.; Patino, F. T.; Roundhill, D. M. Inorg. Chem.
1975, I4, 652. (e) Jeffrey, J. C.; Rauchfuss, T. B. Inorg. Chem.
1979, 18, 2658.

(a) La Placa, S. J.; Ibers, J. A. J. Am. Chem. Soc. 1965, 87, 2581.
(b) Valentine, J. S. Chem. Rev. 1973, 73, 235. (c) Nolte, M. J.;
Singleton, E.; Laing, M. J. Am. Chem. Soc. 1975, 97, 6396. (d)
Vaska, L. Acc. Chem. Res. 197 6, 9, 175. (e) Sen, A.; Halpem, J. J.
Am. Chem. Soc. 1977, 99, 8337. (f) Busetto, C.; D'Alfonso, A.;
Maspero, F.; Perego, G.; Zazzetta, A. J. Chem. Soc., Dalton Trans.
1977, 1828. (g) Ugo, R.; Zanderighi, G. M.; Fusi, A.; Carren', D.
J. Am. Chem. Soc. 1980, 102, 3745. (h) Drago, R. S.; Corden, B.
B.; Zombeck, A. Comments Inorg. Chem. 1981, 1, 53. (i) Suzuki,
M.; lshiguro, T.; Kozuka, M.; Nakamoto, K. Inorg. Chem. 1981,
20, 1993. (j) Poliakoff, M.; Smith, K. P.; Turner, J. J. Wilkinson,
A. J. Chem. Soc., Dalton Trans. 1982, 651. (k) Faller, J. W.; Ma,
Y. Organometallics 1988, 7, 559. (l) Esteruelas, M. A.; Sola, E.;
0ro, L. A.; Meyer, U.; Werner, H. Angew. Chem. Int. Ed. Engl.
1988, 27, 1563. (m)Kitajima, N.; Fujisawa, K.; Morwka, Y.;
Toriumi, K.; J. Am. Chem. Soc. 1989, 111, 8975. (n) Nakamoto,
K. Coord. Chem. Rev. 1990, 100, 363. (o)Egan, J. W.; Haggerty,
B. S.; Rheingold, A. L.; Sendlinger, S. C.; Theopold, K. H. J. Am.
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Mereiter, K.; Schmid, R. J. Chem. Soc., Chem. Commun. 1993,
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Lindner, E.; Speidel, R.; Fawzi, R.; Hiller, W. Chem. Ber. 1990,
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(a) Miller, E. M. and Shaw, B. L. J. Chem. Soc., Dalton Trans.
1974, 480. (b) Jones, C. E.; Shaw, B. L.; Turtle, B. L. J. Chem.
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Empsall, H. D.; Heys, P. N.; Shaw, B. L. J. Chem. Soc., Dalton
Trans. 1978, 257.

CHAPTER II
SYNTHESES AND REACTIVITY STUDIES OF THE F LUXIONAL

PHOSPHINE COMPLEXES
(n3-PR3)M(C0)3 (R = 2,4,6-Trimethoxyphenyl, M = Cr, Mo, W)

18

19

1. Introduction

Reactions of small molecules such as C02, N2, H2, 802, C0, and 02
with transition metal complexes are topics of considerable interest in areas
as diverse as biochemistry, catalysis, and pollution control.1'8 Ligands such
as tertiary phosphines with easily tailored electronic and steric properties
play a key role in research involving stoichiometric and catalytic
transformations of small molecules. The use of ancillary phosphine ligands
for steric control is nicely illustrated in the work of Kubas et al. who
discovered that dihydrogen binds to a five-coordinate metal carbonyl
complex stabilized by the presence of bulky alkyl phosphine groups.4b
Functionalized phosphine ligands that form relatively weak chelate
interactions offer the possibility for coordinative unsaturation without
permanent ligand loss.(r7t 9'12 In particular, ether-phosphine ligands have
been quite useful in mediating the chemistry of transition metals owing to
their tendency to form both a strong metal—phosphorous bond and one or
more weak metal-ether interactions that are readily cleaved in solution.6t7
Unusual features of the ether-phosphine compound tris(2,4,6-
trimethoxyphenyl)phosphine, (T MPP), are its high basicity and the presence
of multiple ether substituents that participate in various bonding modes (n1
to n3, and monometallic to tetrametallic).9 We recently reported the
fluxional carbonyl complex (n3-TMPP)Mo(C0)3 (l) in which the TMPP
ligand displays an n3 binding mode. This unusual compound reacts with
small molecules such as CO with displacement of the ether interactions. In
order to complete the chemistry of group VI metal carbonyls with TMPP, we
report the syntheses of the Cr and W analogues of (n3-TMPP)Mo(C0)3, In
addition to that, reactivity studies of the more stable W analogue with small

molecules have been investigated.

20

2. Experimental Section
A. Physical Measurements

Infrared spectra were recorded on a Nicolet 740 FT-IR
spectrophotometer. 1H NMR spectra were measured on Varian 300— or 500-
MHz spectrometers; chemical shifts were referenced relative to the residual
proton impurity of acetone-d6 (2.04 ppm with respect to TMS). 31P{1H}
N MR spectra were obtained on a Varian 300-MHz spectrometer operating at
121.4 MHz and were referenced relative to an external standard of 85%
phosphoric acid. Elemental analyses were performed at Galbraith
Laboratories, Inc., Knoxville, TN, or Desert Analytics, Tucson, AZ.
B. Synthesis

The starting material (cht)Mo(C0)3 (cht = cycloheptatn'ene, C7H3)
was purchased from Strem Chemicals, Inc and used as received. Tris(2,4,6-
trimethoxyphenyl)phosphine (T MPP) was prepared according to published
methods or purchased from Aldrich and used without further purification.13
W(NCEt)3(C0)3 and Cr(NCEt)3(C0)3 were prepared as described in the
literature.14atb Carbon monoxide was obtained from Matheson Gas Products
and used without further purification. Carbon dioxide, phenylacetylene and
dimethyl acetylenedicarboxylate (Me02CCECC02Me) were purchased from
Aldrich and used without further purification. Acetone was distilled over 3
A molecular sieves or dried by reaction with NaI followed by distillation.
Benzene, diethyl ether, tetrahydrofuran, and toluene were distilled over
sodium-potassium/benzophenone, whereasmethylene chloride was distilled
over P205 under a nitrogen atmosphere. Unless otherwise specified, all
reactions were carried out under an argon atmosphere by using standard

Schlenk-line techniques.

21

(1) Preparation of (nZ-TMPP)M0(C0)4 (2).

(i) Purging of 1 with N2 and H2. A quantity of (TMPP)Mo(CO)3
( 0.200 g, 0.281 mmol) was dissolved in 20 mL of argon-saturated benzene
and the solution was purged with N2 or H2 for 8 h. The resulting yellow
solution was filtered, the volume of the filtrate was reduced under vacuum,
and diethyl ether was added to complete the precipitation. The yellow solid
was washed with 3 x 10 mL of diethyl ether and dried in vacuo; yield 0.138
g (66% based on (TMPP)Mo(CO)3). IR(THF): v(C0) 2017 (m), 1900 (s),
1881 (m, sh), 1841 (m) cm'1. Anal. Calcd for C31H33013PM0: C, 50.28; H,
4.49. Found: C, 50.23; H, 4.43. No intermediates or products containing
dinitrogen or dihydrogen were detected in these reactions including those
performed at low temperatures and in the dark.

(ii) Reaction of l with C0. An amount of (n3-TMPP)Mo(C0)3
(0.120 g, 0.17 mmol) in 20 mL of argon-saturated benzene was purged with
C0 gas at r. t. After 5 min, the volume of the solution was reduced under
vacuum at 50 °C during which time the solution color became noticeably
darker in hue. Hexanes was slowly added to precipitate a yellow solid which
was washed with 3 x 10 mL of hexanes and dried under vacuum; yield 0.098
g (80% based on (TMPP)Mo(CO)3).

(2) Preparation of (nl-TMPP)M0(C0)5 (3).

A solution of (TMPP)Mo(CO)3 (0.200 g, 0.281 mmol) in 8 mL of
benzene was purged with C0 gas for 5 min at room temperature to give a
pale yellow solution. Although (TMPP)Mo(CO)5 cannot easily be isolated
in a bulk solid form due to facile loss of one C0 ligand, its presence in
solution is fully supported by FT-IR, 1H NMR and 31P NMR spectroscopies.
Under these conditions, compounds 1 or 2 are not detected. IR(THF):
v(CO) 2062 (ms), 1973 (w), 1916 (m, sh), 1881 (s)cm'1.

22

(3) Preparation of (TMPP)W(CO)3 (4).

A mixture of W(EtCN)3(CO)3 (0.500 g, 1.154 mmol) and TMPP
(0.615 g, 1.154 mmol) was dissolved in 40 mL of Et20 and stirred for 12 h
to yield a pale yellow solution and a yellow precipitate. The solution was
decanted via cannula techniques, and the precipitate was dried under
vacuum. A yellow compound identified as (T MPP)W(C0)3 (4) was
obtained after recrystallization from argon-saturated CH2CI2 and toluene
(v/v 1/4) in 0.739 g (80% yield based on W(EtCN)3(C0)3). IR(Nujol, cm-
1): v(CO) 1914 (ms), 1769 (5, br). Anal. Calcd for WPC30012H33: C, 45.02:
H, 4.16. Found: C, 43.29; H, 4.10.

(4) Preparation of (TMPP)W(CO)4 (5).

Reaction of 4 with CO. A solution of (T MPP)W(C0)3 (0.150 g,
0.187 mmol) in a mixture of benzene and acetone was purged with C0 gas
for 10 seconds at r. t. This solution was immediately evacuated for a short
period of time (ca. 3 min) to remove excess C0 in order to prevent the
formation of (T MPP)W(C0)5, and then stirred for 1 h under an argon
atmosphere. The volume of the reaction solution was reduced under vacuum
and diethyl ether was added to precipitate a yellow compound, which was
washed with benzene to remove (TMPP)W(CO)5, washed with Et20 and
finally dried in vacuo (0.107 g, 69% yield based on 4). IR (Nujol, cm‘l):
v(C0) 2011 (mw), 1883 (s), 1865 (5, sh), 1822 (s).

(5) Preparation of (TMPP)W(CO)5 (6).

An amount of (TMPP)W(CO)3 (4) (0.150 g, 0.187 mmol) was
dissolved in 35 mL of acetone to yield a clear yellow solution. C0 gas was
purged through the solution for 3 min, which resulted in a gradual color
change from yellow to pale yellow. (TMPP)W(CO)5 was confirmed to be
the sole product by solution FT-IR spectroscopy according to its

23

characteristic pattern in the v(C0) region. The volume of the solution was
reduced under vacuum and hexanes was added to precipitate a pale yellow
solid. The solid was washed with hexanes and dried in vacuo (0.140 g, 88%
yield based on 4). IR(acetone, cm-l): v(C0) 2062 (mw), 1930 (s), 1919 (s),
1880 (m).

(6) Preparation of (TMPP)Cr(CO)3 (7).

A mixture of Cr(EtCN)3(C0)3 (0.500 g, 1.660 mmol) and TMPP
(0.884 g, 1.660 mmol) was dissolved in 40 mL of argon-saturated benzene
and stirred for 12 h. The resulting cloudy red-brown solution was
evaporated to dryness under vacuum. An orange compound identified as
(TMPP)Cr(C0)3 (7) was obtained after recrystallization from argon-
saturated CH2CI2 and toluene in 60% yield (0.666 g) based on
Cr(EtCN)3(C0)3. IR (Nujol, cm'l): v(C0) 1914 (ms), 1794 (5, sh), 1779
(3). Anal. Calcd for CrPC30012H33s0.3(C7H3): C, 55.38: H, 5.13. Found:
C, 55.24; H, 5.21. The quantity of toluene was verified by 1H NMR
spectroscopy.

(7) Preparation of (TMPP)Cr(CO)4 (8).

Reaction of 4 with CO. A solution of (T MPP)Cr(C0)3 (0.150 g,
0.224 mmol) in 15 mL of benzene was purged with C0 gas for 5 seconds at
r.t. to yield a brown solution. The solution was then evacuated for ca. 3 min
to remove excess C0 in order to prevent the formation of (T MPP)Cr(C0)5.
The reaction solution was then treated with an additional quantity of benzene
(20 mL), stirred for 20 min and filtered through Celite to yield an orange
filtrate. The volume was reduced under vacuum and hexanes was added to
precipitate an orange solid, which was washed with hexanes and dried in
vacuo (0.105 g, 67% yield based on 7). IR (Nujol, cm-l): v(C0) 2007 (mw),
1886 (s), 1871 (5, sh), 1826 (s).

24

(8) Preparation of (TMPP)Cr(CO)5 (9).

A solution of (TMPP)Cr(C0)3 (0.150 g, 0.224 mmol) in 10 mL of
benzene was purged with C0 gas for 3 min at r. t. to give a cloudy brown
solution which was filtered through Celite to yield a pale yellow filtrate.
Although (T MPP)Cr(C0)5 cannot be easily isolated in a bulk solid form due
to facile loss of one of the C0 ligands, its presence in solution is fully
supported by IR, 1H and 31P NMR spectroscopies. Under these conditions,
compounds 7 or 8 are not detected. IR (acetone, cm-1): v(C0) 2054 (m),
1970 (w), 1936 (s), 1921 (s), 1886 (ms).

(9) Reactions of (TMPP)M(C0)3 (M = M0, 1; W, 4) with

MeOzCCECC02Me.

(i) Preparation of (TMPP)Mo(CO)3(Me02CCECC02Me) (10).
An excess quantity of Me02CCECC02Me that had been purged with argon
for 2 h before use was introduced into an acetone solution of
(TMPP)Mo(CO)3 (0.200 g, 0.281 mmol) by syringe at -15 °C. An
immediate color change from yellow to orange-red ensued, and the reaction
solution was stirred for 40 min at -15 °C. The solvent was removed by
evaporation under vacuum, and the residue was recrystallized from THF and
hexanes to yield a brown compound. The compound was washed with
hexanes and dried in vacuo (0.101 g, 42% based on 1). IR (Nujol, cm'1)
1997 (m), 1920, (m) 1733 (m), 1697 (m). 1H NMR (acetone-d6): 6 3.54 (s,
C02Me), 3.70 (s, o—0Me), 3.77 (s, C02Me), 3.90 (s, p—0Me), 6.33 (d, m-H).
31P NMR (acetone-d6): 5 1.648 (s).

(ii) Preparation of (T MPP)W(C0)3(Me02CC:-CC02Me) (11).
Excess Me02CCECC02Me that had been purged with argon for 2 h before
use, was added to an acetone solution of (TMPP)W(CO)3 (0.130 g, 0.162
mmol) at -15 °C. A gradual color change from yellow to orange-red

25

occurred within 1 h. The solvent was removed by evaporation under
vacuum, and the solid residue was recrystallized from THF and hexanes to
yield a brown solid which was washed with hexanes and dried in vacuo
(0.136 g, 89% based on 4). IR (Nujol, cm-l) 1996 (m), 1916 (m), 1733 (br).
1H NMR (acetone-d6): 6 3.55 (s, C02Me), 3.70 (s, o-0Me), 3.77 (s,
C02Me), 3.90 (s, p-0Me), 6.33 (d, m-H). 31P NMR (acetone-d6): 6 1.648
(S).

(10) Reactions of (TMPP)Mo(CO)3 with C02.

(i) Without NaPFg. A solution of (TMPP)Mo(CO)3 in argon-
saturated benzene was purged with C02 gas at r. t. The color of the solution
changed from yellow to dark brown within 5 min. After the mixture was
stirred for 12 h, a dark green precipitate and a yellow filtrate were obtained.
A Nujol mull IR spectrum of the dark green precipitate resembles that of the
green precipitate obtained from 02 reactions. The solution IR spectrum of
the yellow filtrate is identical to that of (T MPP)Mo(C0)5.

(i) With NaPF 6 or KBF 4. A solution of (TMPP)Mo(CO)3 in THF or
acetone was purged with C02 gas at -70 °C. No significant color change
was observed after 40 min, therefore the temperature was slowly raised to
r. t. with continual purging with C02 gas for an additional 2 h (alternatively,
the solution can be stirred under a C02 atmosphere for 12 h at r. t.). A
yellow solution was removed from a brown solid and reduced in volume
under an argon purge. Diethyl ether or hexanes was added and the solvent
was removed under a C02 stream or under vacuum to yield a yellow
compound. The compound was identified as a mixture of (TMPP)Mo(CO)4
and a small amount of [CH3-TMPP][PF6] or [CH3-TMPP][BF4] as judged
by IR, 1H, and 31P NMR spectroscopies. The brown precipitate consisted of
unreacted (TMPP)Mo(CO)3 and a PF6- containing species but no carbonyl

26

ligands, which may be [CH3-TMPP][PF6] or [CH3-TMPP][BF4], as
confirmed by IR spectroscopy.
(11) Reaction of (TMPP)W(CO)3 with C02.

A solution of (TMPP)W(CO)3 and KBF4 in 20 mL of acetone was
purged with C02 gas at 0 °C for 30 min. No significant color change was
observed, thus the temperature was slowly raised to r. t.. An intense yellow
solution as well as a pale yellow precipitate were obtained. The solution was
filtered into a Schlenk flask, then layered with hexanes and stored at -5 °C
for 12 h to yield a yellow solid. The solid was redissolved in THF and
hexanes was added to precipitate a yellow compound. The compound was
determined to be (T MPP)W(C0)4 with a small amount of [CH3-TMPP]+
salt as a by-product based on IR, 1H, and 31P NMR spectroscopies.

(12) Reactions of (TMPP)M(C0)3 with 02 (M = M0, 1; W, 4).

A benzene or THF solution of (TMPP)M(C0)3 was purged with 02
gas, which resulted in an immediate color change for 1, and a gradual color
change for 4. A green precipitate with a yellow to pale tan solution were
obtained for molybdenum depending on the reaction times, while a pale
orange precipitate and a yellow solution were obtained for tungsten.

The 02 reactions of M0 were studied by varying the reaction times as
follow: A pale green precipitate and a yellow solution were obtained after
30 min; at this time, (T MPP)Mo(C0)5 was detected as an intermediate in the
solution by IR spectroscopy. After one hour, four carbonyl bands were
observed at 1989 (w), 1925 (wm), 1867 (s), and 1849 (sh) cm‘l. Additional
intense bands in the 1160—1100 cm‘1 region, which have been assigned as
v(0-0) for a superoxo species,15 were observed in the IR spectrum of the
solution phase. X-ray quality single crystals were obtained by slow
diffusion of Et20 into the yellow solution. [IBU4N][BF4] was added in order

27

to exchange the [CH3-TMPP]+ ion with [’Bu4N]+ ion. The compound was
determined to be [’BU4N]4[MO3026], the salt containing the well—known
polyoxometalate ion [M08026]4‘, by X-ray crystallography. With longer
reaction times, a green precipitate was obtained along with a yellow solution
with a more complicated carbonyl IR regim. After 4.5 h, a green precipitate
and a pale tan solution with an absence of carbonyl stretching vibrations in
the IR spectrum was obtained.

A pale orange precipitate and a yellow solution results from the
reaction of (TMPP)W(CO)3 with 02. Only phosphonium salts such as [H-
TMPP]+ and [CH3-TMPP]+ were detected in the pale orange precipitate, as
determined by 1H and 31P NMR spectroscopies. (TMPP)W(CO)5 was
identified as an intermediate in the yellow solution by IR spectroscopy.

(13) Reactions of (TMPP)M(CO)3 with 802 (M = M0, 1; W, 4).

(i) Solution Reactions. A solution of (T MPP)M(C0)3 in various
solvents such as THF, toluene, acetone, and benzene was purged with 802
gas; alternatively, (T MPP)M(C0)3 was dissolved in 802 saturated solvents
at different temperatures. All the reactions produce an immediate color
change from yellow to reddish-brown with heat evolution. An IR spectrum
of the solution phase revealed product bands in the range 1100-1350 cm'l,
which are indicative of n 1-pyrimidal or nz- binding modes of 802 ligand for
a (16 metal center.5

(ii) Solid State Reactions. An amount of (T MPP)W(C0)3 was
loaded in a Schlenk flask and purged with 802 gas whereupon an immediate
reaction occurred. The solid was observed to change from a yellow powder
to a reddish—brown oil. The oil was washed with toluene and dried under
vacuum to yield a reddish-brown solid. A Nujol mull IR spectrum of the

compound revealed a carbonyl stretching pattern silmilar to that of

28

(TMPP)W(CO)5 and a complicated pattern in the region for v(SO2) due to a
coincidence with bands for the TMPP ligand.

(iii) NMR Solution Reactions. An solution of (TMPP)Mo(CO)3 in
acetone-d5 was purged with 802 for 2 min at 0 °C, which resulted in an
immediate color change from yellow to reddish-brown, and monitored by 1H
N MR spectroscopy. [H-TMPP]+ was detected as a major species along with
(TMPP)Mo(C0)4 and (T MPP)Mo(C0)5 which appeared within 5 min. [H-
TMPP]+ is the only NMR active product observed for reaction times
exceeding 10 min. This indicates that reaction product (or products) may be
paramagnetic, and, as such, may be NMR inactive with [H--TMPP]+ as a
counterion.

C. X-ray Crystallographic Studies

Crystallographic data for compounds 2 and 3 were collected on a
Rigaku AFC6S diffractometer, while 7oCH2CI2 and 8 were collected on a
Nicolet P3N diffractometer equipped with monochromated Mo Ka
radiation; a 2 KW sealed tube generator was used for the former, while a 3
KW sealed tube generator was for the latter. Crystallographic computing
was performed on a VAXSTATION 4000 by using the Texsan
crystallographic software package of Molecular Structure Corporation.16
Crystal parameters and basic information pertaining to data collection and
structure refinement are summarized in Tables 2.1 and 2.2.

(l) (nZ-TMPP)M0(C0)4 (2). Single crystals of 2 were grown from an
acetone-d5 solution of the compound at 0 °C. A yellow crystal of
dimensions 0.59 x 0.39 x 0.57 mm3 was secured on the tip of a glass fiber
with Dow Corning silicone grease and placed in a cold N2(g) stream. Least-

squares refinement using 22 well-centered reflections in the range

29

Table 2.1. Summary of crystallographic data for (TMPP)Mo(C0)4 (2)

 

 

and (TMPP)Mo(CO)5 (3).

2 3
formula MoP013C31H33 MoP014C32H33
formula wt 740.51 768.52
space group P21/n P21/n
a, A 12.222 (3) 11.232 (3)
b, A 17.756 (8) 23.250 (7)
c, A 15.342 (2) 13.515 (4)
01, deg 90 90
1:3, deg 97.94 (2) 103.79 (2)
v. deg 90 90
V, A3 3297 (2) 3428 (2)
Z 4 4
dclac, g/cm3 1.492 1.489
11, cm-1 4.96 4.82
temp, °C -90i1 -90i1
trans factors, max., min 1.00, 0.87 1.00, 0.88
Ra 0.032 0.032
wa 0.046 0.043

 

a R = XllFol - chII/ZlFol- b Rw = [XWIFoI - ch|)2/ ZWlFo|21 1’2; W = 1/02(|Fo|)-

30

Table 2.2. Summary of crystallographic data for (TMPP)Cr(C0)3 (7),

 

 

(TMPP)Cr(CO)4 (8).

7-CH2C12 8
formula CrPC12012C31H35 CrP013C31H33
formula wt 753.49 696.56
space group P21/c P21/n
a, A 16.758 (4) 12.009 (4)
b, A 11.813 (3) 17.745 (5)
c, A 16.949 (6) 15.257 (4)
01 deg 90 90
6, deg 95.61 (2) 97.63 (2)
11, deg 90 90
V, A3 3339(3) 3223 (3)
Z 4 4
dclac, g/cm3 1.499 1.436
1.1, cm—l 6.01 4.56
temp,°C -85i2 -90i1
trans factors, max., min. 1.00, 0.71 1.00, 0.94
Ra 0.047 0.043
wa 0.047 0.041

 

a R = XllFol - chll/ZIFoI. 1’ Rw = [XWIFoI - chlF/ZWIFoIZI 1’2; W = 1/02(lFol)-

31

33 S 20 S 39° indicated that the crystal belonged to a monoclinic crystal
system. The data were collected at - 90 i 1 °C using the 00-20 scan
technique to a maximum 20 value of 50°. 0f the 6318 reflections that were
collected, 6023 were unique. An empirical absorption correction based on
azimuthal scans of three reflections was applied which resulted in
transmission factors ranging from 0.87 to 1.00. The data were corrected for
Lorentz and polarization effects. The space group was determined to be
P21/n based on the observed systematic absences. The structure was solved
by PHASE and followed by DIRDIF structure solution programs and refined
by full-matrix least-squares refinement.17 All non-hydrogen atoms were
refined anisotropically. The final full-matrix refinement was based on 4235
observed reflections with F 02 > 30(F02) that were used to fit 547 parameters
to give R = 0.032 and Rw = 0.046. The goodness-of—fit index was 1.29, and
the highest peak in the final difference map was 0.33 e'/ A3.

(2) (T MPP)M0(CO)5 (3). Single crystals of 3 were grown by slow
diffusion of hexanes into a C0-saturated benzene solution of the compound
at room temperature. A pale-yellow crystal of dimensions 0.54 x 0.31 x 0.34
mm3 was mounted on the tip of a glass fiber with Dow Corning silicone
grease and placed in a cold N2(g) stream. Least-squares refinement using 18
well-centered reflections in the range 29 S 20 S 30° gave a cell
corresponding to a monoclinic crystal system. A total of 6524 data (6194
unique) were collected at -90 i 1 °C using the 00-20 scan technique to a
maximum 20 value of 50°. An empirical absorption correction based on
azimuthal scans of three reflections with x near 90° was applied which
resulted in transmission factors ranging from 0.88 to 1.00. The data were
corrected for Lorentz and polarization effects. Systematic absences from the

data led to the choice of P21/n as a space group. The structure was solved by

32

MITHRIL and followed by DIRDIF structure solution programs and refined
by full-matrix least-squares refinement.18 The final full-matrix refinement
was based on 4954 observations with F02> 30(F02) and 565 parameters to
give R = 0.032 and Rw = 0.043. The goodness-of—fit index was 1.94, and the
highest peak in the final difference map was 0.45 e'/A3.

(3) (T MPP)Cr(CO)3-CH2C12 (7)-CH2C12. X-ray quality crystals of
(T MPP)Cr(C0)3 (7) were obtained from a slow diffusion of diethyl ether
into an argon-saturated CH2C12 solution of the title compound at 0 °C. An
orange crystal of dimensions 0.18 x 0.41 x 0.13 mm3 was selected and
secured on the end of a glass fiber and placed on the goniometer in a N2(g)
cold stream at - 85 :1: 1 °C. Cell constants and an orientation matrix for data
collection obtained from a least-squares refinement using the setting angles
of 36 carefully centered reflections in the range 4.19 < 20 < 28.04°
corresponded to a monoclinic cell. A total of 5442 data were collected using
the 00-20 scan technique to a maximum 20 value of 47°. An empirical
absorption correction based on azimuthal scans of three reflections with x
near 90° was applied which resulted in transmission factors ranging from
0.71 to 1.00. The data were corrected for Lorentz and polarization effects.
Systematic absences from the data led to the choice of P21/c as a space
group. The structure was solved by MITHRIL and followed by DIRDIF
structure solution programs and refined by full-matrix least-squares
refinement.18 The final full-matrix refinement was based on 2688
observations with F02> 30(F02) and 424 parameters to give R = 0.047 and
Rw = 0.047. The goodness-of-fit index was 1.36, and the highest peak in the
final difference map was 0.35 e‘/A3.

(4) (TMPP)Cr(CO)4 (8). X-ray quality crystals of (T MPP)Cr(C0)4 (8)

were obtained from a slow diffusion of hexanes into an acetone solution of

33

the title compound. An orange crystal of dimensions 0.21 x 0.39 x 0.18
mm3 was selected and secured on the end of a glass fiber and placed on the
goniometer in a N2(g) cold stream at - 90 i 1 °C. Cell constants and an
orientation matrix for data collection obtained from a least-square
refinement using the setting angles of 25 carefully centered reflections in the
range 15.06 < 20 < 27.27° corresponded to a monoclinic cell. A total of
5249 data (4987 unique) were collected using the 00-20 scan technique to a
maximum 20 value of 47°. An empirical absorption correction based on
azimuthal scans of three reflections with x near 90° was applied which
resulted in transmission factors ranging from 0.94 to 1.00. The data were
corrected for Lorentz and polarization effects. Systematic absences from the
data led to the choice of P21/n as a space group. The structure was solved by
MITHRIL followed by DIRDIF structure solution programs and refined by
full-matrix least-squares refinement.18 The final cycle was based on 2589
observations with F02> 30(F02) and 415 parameters to give R = 0.043 and
Rw = 0.041. The goodness-of-fit index was 1.31, and the highest peak in the
final difference map was 0.33 e‘lA3.

3. Results and Discussion

A. Syntheses of (n3-TMPP)M(C0)3 (M = W, 4; Cr, 7).

Transition metal complexes possessing an unsaturated coordination
environment and functionalized ligands that provide vacant coordination
sites without permanent ligand loss are good candidates for small molecule
reactions. The use of coordinatively unsaturated compounds was well
illustrated by Kubas and co-workers who isolated the first recognized
dihydrogen adduct from the reaction of an unsaturated metal carbonyl
phosphine complex with H2413 The use of polydentate ligands such as
tripodal12 and functionalized phosphines (P,O)6-7, 9‘12 play an important

34

role in catalysis. Most of the functionalized phosphines (P,0) are not as
flexible as desired which limits the possibilities for reversible coordination
of molecules. The results outlined in this chapter demonstrate that TMPP
can bind to a metal in a variety of modes (n1 to 113, and monometallic to
tetrametallic),9 which allows the metal to adjust its electron count and steric
requirements by loss or gain of bonds to pendant ether groups.

With the use of TMPP, we sought to synthesize the chromium and
tungsten analogues of the tricarbonyl compounds (n3-TMPP)M(C0)3 (M =
Cr, W), with the ultimate goal of investigating the entire series of group VI
tricarbonyl compounds (n3-TMPP)M(C0)3 with key small molecules.
Unlike the situation with the Mo analogue, the reaction of Cr(cht)(C0)3 (cht
= cycloheptatriene) with TMPP fails to give (n3-TMPP)Cr(C0)3 (7), but
instead produces low yields of (nZ-TMPP)Cr(C0)4 (8). Kubas et al.
reported a similar problem with the attempted preparation of
Cr(C0)3(PCy3)2 (PCy3 = tricyclohexyl phosphine) from Cr(C0)3(cht).4h
The eventual successful synthesis of Cr(C0)3(PCy3)2 from the reaction of
Cr(C0)3(naphthalene) with PCy3 by Hoff and coworkers demonstrated that
the naphthalene ligand is a better leaving group than the cycloheptatriene
ligand, results that correlate well with theoretical studies of these two
ligands. 19 Our work also required the use of more reactive starting
materials for the syntheses of (n3-TMPP)M(C0)3 (M = W, 4; Cr, 7), thus
we turned to reactions of the more labile compounds M(C0)3(NCEt)3 (M =
Cr, Mo, W) (EQ, 2.1), which have been used extensively for the synthesis of

tricarbonyl metal complexes.

 

M(CO)3(NCEt)3 + TMPP r (TMPP)M(CO)3 (2.1)

(M = Cr, W)

35

Room temperature 1H NMR spectra of both compounds revealed
broad, unresolved resonances which indicated that the molecules were
fluxional as had been previously found for the molybdenum analogue.99
Details of the solution N MR behavior of the two compounds as well as the
structural determination of (T MPP)Cr(C0)3 (7) are discussed in Section B.
B. Carbonylation Reactions of (TMPP)M(C0)3 (M = M0, 1; W, 4;

Cr, 7).

(1) Syntheses. Reversible reactions involving thermal and
photochemical lability of CO from ether-phosphine complexes have been
documented in the literature.6a7e Irreversible reactions such as those
involving the conversion of 1 to 2 were reported by Verkade and co-workers
who developed a new class of group VI metal carbonyl complexes of the
type fac-(P,P',0)M(C0)3 that react with a variety of substrates (e. g., C0, py,
MeCN) via irreversible dissociation of the metal-oxygen bond.10 In our
studies, the pentacarbonyl derivatives (11 1-TMPP)M(C0)5 (M = M0, 3; W,
6; Cr, 9) were observed to form in the reaction between (n3-TMPP)M(C0)3
(M = M0, 3; W, 6; Cr, 9) and excess carbon monoxide, but they reversibly
lose one equivalent of C0 in the absence of a C0 atmosphere to yield the
more stable molecules (n 2-TMPP)M(C0)4 for the chromium and
molybdenum complexes. In the case of 6, the reaction to form 5 is
irreversible.

In related studies aimed at isolating N2 or H2 adducts of (n 3-
TMPP)Mo(C0)3 1, we discovered, to our complete surprise, that the major
isolable product was (nZ-TMPP)Mo(C0)4 2, generated in ~ 65% yield from
solutions of 1 saturated or purged with N2 or H2 gas. The identical result
was obtained for W and Cr. The formation rate of (TMPP)M(C0)4 by this

method, however was seen to vary with metal identity. The reaction rate

36

decreases in the series M = Cr > Mo > W. Curiously, we were not
successful at isolating or even detecting N2 or H2 containing intermediates
or products, in spite of our efforts which included the use of 15N2 labelling,
low temperatures and the exclusion of light. Solutions of 1 purged with
argon or stored under an argon atmosphere for a long period of time also
eventually produce 2, but the transformation occurs much more slowly than
solutions exposed to an atmosphere of N2 or H2. The presumed fragment
"Mo(TMPP)" resulting from complete loss of CO from some of the
molecules may be producing finely divided Mo metal and TMPP or a
paramagnetic Mo/TMPP compound. Although free TMPP was not observed
in the 1H NMR spectra of residues taken from the mother liquid, the
phosphonium cations [H-TMPP]+ and [CH3-TMPP]+, which are ubiquitous
species in TMPP decomposition chemistry, were identified. The possibility
of trace 02 in these gases giving rise to these results occurred to us, therefore
we carried out deliberate reactions of 1 with 02 in different solvents and
under a variety of reaction conditions in order to test this hypothesis.
Reactions between 1 and small quantities of 02 result in an immediate color
change from yellow to cloudy yellow-green with the deposition of a green
precipitate. The green solid does not exhibit carbonyl stretches whereas the
yellow filtrate exhibits v(C0) bands characteristic of (nl-TMPP)M0(C0)5
but none that can be attributed to (112-TMPP)Mo(C0)4. With longer
reaction times, the chemistry of 1 with 02 proceeds further to give a pale tan
solution that is inactive in the v(C0) region along with the green precipitate.
We take these collective results to be good evidence for the lack of
participation of trace 02 impurities in the N2 and H2 gases. Attempts to

solve this problem by employing the more stable W derivatives also failed.

37

While the complete loss of C0 ligands from arene tricarbonyl
compounds of M0 is known to occur, the apparent loss of C0 facilitated by
N2 and H2 is highly unusual. Evidently the combination of a single highly
basic phosphorus donor and two ether groups is not well suited for the
stabilization of the Mo(C0)3 core. In contrast, the tetracarbonyl derivative,
is quite stable as judged by its ease of formation from both the tri and
pentacarbonyl derivatives.

Carbonylation of 4 (W) and 7 (Cr) produces the pentacarbonyl
derivatives 6 and 9, respectively. The former (TMPP)W(CO)5 is stable in
the absence of a C0 atmosphere, whereas the latter (TMPP)Cr(CO)5
converts to the tetracarbonyl. In fact, (TMPP)W(CO)5 is so stable that it
will not convert to the tetracarbonyl derivative (TMPP)W(CO)4 even when
heated in vacuo and is therefore observed to form under a variety of reaction
conditions under which C0 can be scavenged. The synthesis of
(TMPP)W(CO)4 (5), then, requires that the reaction of (T MPP)W(C0)3 (4)
be performed with a limited quantity of C0. (T MPP)W(C0)4 can also be
obtained in low yield from solution of 4 treated with nitrogen, but the
reaction rate is much slower than that for the Mo reaction and the
methylphosphonium salt [CH3-TMPP]+ is formed as a by-product of the
reaction. (T MPP)Cr(C0)4 (8) is best obtained from the reaction of
(TMPP)Cr(C0)3 (7) with a limited quantity of C0, due to the fact that the
conversion of (T MPP)Cr(C0)5 to (TMPP)Cr(CO)4 under vacuum is
incomplete. Under thermal conditions, the attempted conversion of
(TMPP)Cr(CO)5 to (T MPP)Cr(C0)4 leads to decomposition. Reactions that
involved liberation of CO from solutions of (TMPP)Cr(C0)3 do not cease at
the formation of (TMPP)Cr(CO)4, as both (TMPP)Cr(CO)4 and
(TMPP)Cr(CO)5 are detected in solutions for longer reaction time (8 hours

38

in benzene). This is not the case, however, for reactions of tricarbonyl metal
complexes with nitrogen (M = M0 and W) unless the reaction times are
extremely long (3 - 5 days). The stabilities of the members of this series
may be rationalized by considering that the pentacarbonyl complexes
experience the most steric hindrance due to the presence of one TMPP
molecule and five carbonyl ligands compared to the corresponding tetra-
(four carbonyls) and tricarbonyl (three carbonyls) derivatives. In addition,
metal identity obviously plays a role as well, if one considers that, due to the
larger size of W atom compared to another two metals (Mo and Cr),
(T MPP)W(C0)5 is the only stable species found in the pentacarbonyl
system; this compound does not reversibly convert to the corresponding
tetracarbonyl derivative which the others readily do. Carbonylation
reactions of these tricarbonyl compounds are summarized as shown in
Scheme 2.1.

(2) NMR Studies of 2-9. NMR spectroscopic data for 2-3, 4—6, and
7-9 are summarized in Tables 2.3 - 2.5, respectively. Room temperature 1H
NMR spectra of tri- and tetracarbonyl compounds 2, 4, 5, 7, and 8 consist of
broad and featureless resonances, an indication of a dynamic process
occurring in solution. Variable temperature 1H NMR spectra of 2, 4, 5, 7,
and 8 (Figures 2.1 - 2.5 respectively) were obtained from +20 to -80 °C in
acetone-d6, these results support the conclusion that all three arene rings are
participating in a fluxional process. The low temperature spectrum of 2
( Figure 2.1) at -80 °C reveals nine distinct resonances between 34.5 ppm
that are due to the inequivalent ortho- and para-methoxy groups and
overlapping resonances between 6-6.5 ppm attributed to the meta protons.
Similar phenomena were observed for compounds 5 and 8 as shown in

Figures 2.3 and 2.5. The low temperature spectra of 4 (Figure 2.2) and 7

39

l. M =Cr,Mo

2C0

 

 

(TMPP)M(C0)3 4 (TMPP)M(C0)5
- C0
+ C0 + CO
(TMPP)M(CO)4
2. M = W
(TMPP)M(C0)3 2 C0 + (TMPP)M(C0)5
4 5
+x %:
(TMPP)M(C0)4
6

Scheme 2.1. Carbonylation of (TMPP)M(C0)3.

40

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PPM

 

 

Figure 2.2. Variable temperature 1H NMR spectra of (T MPP)W(CO)3 (4)
in acetone-d6.

45

 

4 +20 °C
i K"\________

 

Figure 2.3. Variable temperature 1H NMR spectra of (T MPP)W(CO)4 (5)
in acetone-d6.

46

 

+20

 

F,

 

 

 

 

 

 

 

 

0°C
J -20°C

P
m m 40°C
-60°C
+IIWIITIIITIIIITIIIIIIIIIIIIIIIIIIIIIII[I
6.5 6 5.5 5 4.5 4 3.5 3

ppm

Figure 2.4. Variable temperature 1H NMR spectra of (TMPP)Cr(CO)3 (7)
in acetone-d6.

47

+20 °C

°C

 

i r

20 °C

 

°C

 

“C

I I I I I r I 1 fl I I I I T f I I I I I l I I I I I I I I I I I 1+
6.4 6 5.6 5.2 4.6 4.4 4 3.6 3.2
PM"

 

Mé-Hl - -

Figure 2.5. Variable temperature 1H N MR spectra of (T MPP)Cr(CO)4 (8)
in acetone-d5.

48

(Figure 2.4) at -20 °C and -50 °C respectively, reveal five distinct
resonances between 3.3-4.5 ppm that are due to three inequivalent ortho-
and two para-methoxy groups and three resonances between 6-6.5 ppm
attributed to three inequivalent sets of meta protons.

An MNR solution of 3 was prepared by loading an acetone-d6
solution of 2 in a NMR tube in the dry box, followed by capping with a
rubber septum and purging with CO gas for 5 minutes. A similar procedure
was followed to obtain a solution of 9 for NMR spectral measurements. A
room temperature 1H NMR spectrum of 3 exhibits only three resonances;
one for the six ortho-methoxy groups, a second for the three para-methoxy
groups and a third signal for the six equivalent meta protons. Variable
temperature 1H N MR data (Figure 2.6) for 3 support equivalence of all three
rings down to -60 °C; these data are compatible with the solid-state structure
wherein the TMPP ligand is involved in n1 binding to the Mo center, a
situation that allows for free rotation about the Mo-P bond. Similar NMR
solution behavior was observed for compounds 6 and 9.

A comparison of the low temperature limiting 1H NMR spectra for the
three types of compounds in the methoxy region (3-5 ppm) reveals the
usefulness of this tool for the assignment of TMPP binding modes in
solution (Scheme 2.2). Five distinct resonances observed for tricarbonyl
metal complexes, designated as (a)-(c) are due to three inequivalent sets of
ortho methoxy groups, whereas two signals ((1), (e) are anticipated on the
basis of two magnetically inequivalent para methoxy groups. The nine
methoxy resonances observed for tetracarbonyl metal complexes designated
as (a)-(i) are assigned to all inequivalent ortho and para methoxy groups.
Interestingly, this spectrum points to a rigid Mo—P—C-C-O metallacycle, as a

dynamic process involving a "flipping" of the envelope orientation would

49

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51

effectively render the two free arene rings equivalent, thereby leading to the
observation of only three resonances for both rings instead of six signals.
Finally, only two resonances occur in the ortha and para methoxy region of
pentacarbonyl metal complexes, designated as (a) and (b); these are assigned
to six equivalent ortha methoxy groups and three equivalent para methoxy
substituents.

31P NMR spectral measurements performed on compounds 1, 2 and 3
revealed single resonances whose chemical shift values reflect an increase in
shielding with increasing numbers of carbonyl ligands. The signals appear
at 5 -1.13, -10.6 and -27.4 ppm for compounds 1, 2 and 3 respectively, in
accord with decreased metal-phosphorus overlap in the same order (vide
infra). The same trend was observed for the Cr and W derivatives. For W,
the signals appear at 6 +17.74, -10.08 and -45.70 ppm for compounds 4, 5
and 6 respectively. For Cr, the signals appear at 5 +1853, +10.31 and -1.53
ppm for compounds 7, 8 and 9 respectively. This complete compilation of
31P NMR resonances for the nine compounds provides a nice illustration of
shielding effects for group VI metal carbonyl compounds in going from the
first row (Cr) to the third row (W). N

(3) Molecular Structures of 2, 3, 7 and 8. ORTEP drawings and
selected bond distances and angles for compounds 2, 3, 7 and 8 are
presented in Figures 2.7 - 2.10 and Tables 2.6 - 2.9, respectively. All four
molecules exhibit a distorted octahedral geometry about the metal center,
with the TMPP ligand being coordinated to the Mo atom in bonding modes
of n3 in 7, n2 in 2 and 8, and n1 in 3. The geometrical distortions observed
in tri- and tetracarbonyl compounds are a consequence of the strained five-
membered metallacyclic rings of the type M-P—C—C-O. The non-ideality of
the structure is best illustrated by the angles Pl-Mol-Ol = 74.36 (6) ° in 2,

52

 

Figure 2.7. ORTEP drawing of (TMPP)Mo(CO)4 (2).

Table 2.6. Selected bond distances (A) and bond angles (°) for

 

 

 

 

 

(TMPP)Mo(CO)4 (2).

Bond Distances
A B A-B (A) A B A-B (A)
Mol P1 2.551 (1) C28 010 1.149(5)
Mo] 01 2.317(2) C29 011 1.153(5)
Mol C28 1.941 (4) C30 012 1.139 (5)
Mo] C29 2.034 (4) C31 013 1.157 (5)
Mol C30 2.031 (4) P1 C7 1.836 (4)
Mol C31 1.965 (4) P1 C16 1.819(4)
01 Cl 1.425 (5) P1 C26 1.823 (3)

Bond Angles

A B C A-B-C (°)
P1 M01 01 74.36 (6)
P1 Mol C28 98.2 (1)
P1 Mol C29 99.3 (1)
P1 Mol C30 87.4 (1)
P1 Mol C31 171.6(1)
Mol P1 C7 128.0(1)
Mol P1 C16 108.0(1)
Mol P1 C26 100.3 (1)

 

54

 

Figure 2.8. ORTEP drawing of (T MPP)Mo(C0)5 (3).

Table 2.7. Selected bond distances (A) and bond angles (°) for

 

 

 

 

 

(TMPP)Mo(CO)5 (3).

Bond Distances
A B A-B (A) A B A-B (A)
Mol P1 2.6364(9) C81 081 1.142 (4)
Mol C80 2.050 (4) C82 082 1.135 (4)
Mol C81 2.062(3) C83 083 1.137 (4)
Mol C82 2.052 (3) C84 084 1.145 (4)
Mol C83 2.041 (4) P1 C1 1.848(3)
Mol C84 1.974 (3) P1 C7 1.840(3)
C80 080 1.124 (4) P1 C13 1.847 (3)

Bond Angles

A B C A-B-C (°)
P1 Mol C80 90.6 (1)
P1 Mol C81 95.46 (9)
P1 Mol C82 85.15 (9)
P1 Mol C83 91.80 (9)
P1 Mol C84 178.0 (1)
Mol P1 Cl 121.77 (9)
Mol P1 C7 99.86 (8)
Mol P1 C13 120.19 (9)

 

56

 

Figure 2.9. ORTEP drawing of (T MPP)Cr(C0)3 (7).

Table 2.8. Selected bond distances (A) and bond angles (°) for
(TMPP)Cr(CO)3-CH2C12 (7)-CH2C12.

 

 

 

 

 

Bond Distances
A B A-B (A) A B A-B (A)
Crl P1 2.330 (2) C31 031 1.174 (7)
Crl 01 2.048 (4) C32 032 1.174 (7)
Crl 07 2.218 (4) C33 033 1.156(7)
Crl C31 1.831 (7) P1 C1 1.824(6)
Crl C32 1.809 (7) Pl C7 1.809 (6)
Crl C33 1.827 (7) P1 C13 1.825 (6)
01 C19 1.437 (7) 07 C25 1.448(7)

Bond Angles

A B C A-B-C (°)
P1 Crl 01 78.9 (1)
P1 Crl 07 75.1 (1)
P1 Crl C31 174.1 (2)
P1 Crl C32 94.0 (2)
P1 Crl C33 98.5 (2)
Crl P1 C1 103.6 (2)
Crl P1 C7 123.0 (2)
Crl P1 C13 104.1 (2)

 

58

 

 

 

Figure 2.10. ORTEP drawing of (TMPP)Cr(CO)4 (8).

Table 2.9. Selected bond distances (A) and bond angles (°) for

59

 

 

 

 

 

(TMPP)Cr(CO)4 (8).
Bond Distances
A B A-B (A) A B A-B (A)
Crl P1 2.413 (2) C41 041 1.165 (6)
Crl 03 2.198 (4) C42 042 1.159 (6)
Crl C41 1.836(6) C43 043 1.171 (6)
Crl C42 1.883 (6) C44 044 1.150 (6)
Crl C43 1.819 (6) P1 C1 1.812 (5)
Cr] C44 1.897 (6) P1 C7 1.840(5)
03 C21 1.42346) P1 C13 1.817 (5)
Bond Angles

A B C A-B-C (°)
P1 Cr] 03 74.6 (1)
P1 Crl C41 172.6 (2)
P1 Crl C42 88.2 (2)
P1 Crl C43 96.5 (2)
P1 Crl C44 99.0 (2)
Crl P1 C1 100.2 (2)
Crl P1 C7 128.1 (2)

31 P1 C13 109.0 (2)

 

60

Pl-Cr1-03 = 74.6 (1) ° in 8, and Pl-Crl-Ol = 78.9 (1) ° and P1-Cr1-07 =
75.1 (1) ° in 7. The ease of conversion of tricarbonyl compounds to the
more stable tetracarbonyl compounds may be a result of relieving ring strain
in one of the two metallacycles described above. The coordination of five
carbonyl ligands in 3 allows for a monodentate binding mode for TMPP and
therefore no strained chelate is present.

The Mo-P distance in (TMPP)Mo(CO)5 is 0.085 A longer than that in
(nZ-TMPP)M0(C0)4 and 0.16 A longer than that in (n3-TMPP)M0(C0)3,
while the Cr-P distance in (nZ-TMPP)Cr(C0)4 is 0.083 A longer than that of
(n3-TMPP)Cr(C0)3. This trend reflects a combination of several influences
all operating in the same direction; these are the chelate effect contributed by
the TMPP ligand in tri- (n3-) and tetracarbonyl 012-) compounds, the effect
on the Mo—P bonding of replacing poor ether donors with the more strongly
bonded carbonyl ligands, and the steric effects in going from three to five
carbonyl ligands in a six-coordinate molecule that contains a bulky tertiary
phosphine. The Mo-P distance in 3 (2.6364 A) is longer than the bond
distances reported in other LMo(C0)5 complexes (2.37-2.56 A)20a,c,d
whereas the Mo-P distance in 2 (2.551 A) is in the range 2.49-2.58 A found
for (L~L)Mo(C0)4 and L2Mo(C0)4 complexes (L = a monodentate
phosphorus ligand and L~L = a bidentate phosphorus ligand).20‘1‘b The Cr-P
distance in 8 (2.413 A) is in the range 2.35-2.42 A found for LL'Cr(C0)4 or
L2Cr(C0)4 complexes (L = a monodentate phosphorus ligand).20 The Cr-P
distance in 7 (2.330 A) is in the range 2.35-2.42 A reported for fac-
L3Cr(C0)3 complexes (L = a monodentate phosphorus ligand) and
compounds of the type fac, fac—(triphos)Cr2(C0)(,.2051,f The MC distances
within each molecule are inequivalent, with the M-C distances of the

carbonyl ligand trans to the P atom being the shortest in 2, 3 and 8 (see

61

Tables 2.6, 2.7 and 2.9); this result agrees with the corresponding distances
reported for similar molecules such as cis-LL'Mo(C0)4, cis-L2Mo(C0)4 and
M(CO)5(L) (M: Cr, Mo) complexes.20b'd The shorter Mo-C bond opposite

the P donor for 2 and 3 is explained on the basis of increased ir-backbonding
from the basic phosphorus donor to this C0 ligand. The Mo-C distances in
1 and 7, however, do not fit this trend; in fact the M-C distance for the
carbonyl ligand trans to phosphorus atom is the longest M-C distance in 1
and 7 which suggests a dominant o trans-effect that can be rationalized on
the basis of effective mixing of filled (in orbitals for these pseudo-C3
symmetry molecules which would tend to average the n—backbonding effects
among the three C0 ligands. This conclusion is supported by the recently
reported X-ray structure of (L3)W(C0)3 where L3 = a tripod N ,P,S ligand in
which the W-C bond opposite the phosphorus donor is longer than the other
two W-C distances, a result that the authors attribute to a trans effect.206
C. Reactions of (TMPP)M(C0)3 with Substituted Acetylenes (M =
M o, 1; W, 4).
The methyl-phosphonium salt [CH3-TMPP]+ was detected as the only
identifiable product from the reaction of (T MPP)M(C0)3 with PhCZ-CH,
while a compound formulated as (TMPP)M(C0)3(Me02CCECC02Me) was
Obtained in the reactions with Me02CCECC02Me. This conclusion is based
on collective data obtained from IR, 1H, and 31P NMR spectroscopies. The
1H NMR spectrum (Figure 2.11) consists of two sharp singlet resonances
and one doublet that are assigned to the TMPP ligand in its 111-bonding
mode (See Section B), while two distinct resonances are assigned to the two
methyl groups of Me02CCECC02Me (TMPP and Me02CCECC02Me in 1
. 1 1”Eltio based on integration). The average C0 frequencies for
(TWP)M(C0)3(Me02CC_=CC02Me) are ca. 70100 em-l higher than that

62

.AoENOUUMUUNOoEvaOUvoZAmn—ZC .«o 82.30qu 522 =_ .:.N 0.59...—

 

 

 

 

 

 

63

of (T MPP)M(C0)3, which indicates that Me02CCECC02Me acts as an 71-
electron acceptor. The difference between the two terminal methyl groups
of the acetylene ligand as observed by 1H NMR spectroscopy is useful for
predicting the structure of the compound. Based on the above information,

the coordination geometry of the compound is proposed to be five-
coordinate (n1-TMPP)M(C0)3(Me02CCECC02Me).

PhC=—_— CH

 

 

 

 

co
..-“CO .. ~“CO .H
P—w' co ———> —w'—-C-—--c"
\
k P/ Kp/ I Ph
co co

A proposed pathway for the alkyne reaction is presented in Scheme
2.3. Compound A is obtained as an intermediate from the reaction of
(T MPP)M(C0)3 with Me02CCECC02Me, which quickly converts to more
stable compound B to release the steric hindrance caused by the repulsion
between the incoming alkyne ligand and the nZ-TMPP moiety. Compound
B undergo isomerization to form a vinylidene metal phosphine complex (C
or D), as it is known terminal alkynes can undergo isomerization to form
vinylidene complexes in order to eliminate metal dtr-ligand par repulsion
resulting from a lack of vacant dir orbitals for octahedral (16 metal
complexes, as shown below.21 The electron-withdrawing substituents on the
alkyne ligands can lower the energy of the alkyne 7r*// orbitals in order to

enhance metal (171’ backbonding and stabilize the reaction adducts by
delocalizing the it .L electron pair away from the filled metal (171' orbital to

decrease the antibonding d7r-1r 1 conflicts.21 The two C02Me groups on the

bound alkyne experience different environments due to their proximity to the

64

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65

TMPP ligand on one side and carbonyl group on the other side, which results

in two distinct resonances as seen in Figure 2.11.

D. Oxygenation Reactions of (TMPP)M(C0)3 (M = M0, 1; W, 4).
Dioxygen adducts of transition metal complexes are rare due to their

inherent instability.8 Molecular oxygen is known to be a good oxidant with

oxygen transfer to ancillary ligands such as these depicted below.

M(SOZ) M(SO4)
M(CO) 02 M(C03)
M(PR3) —_' M(OPR3)
M(NO) M(N03)

We have investigated the chemistry of (T MPP)M(C0)3 with 02 to
probe the possibility of forming kinetic products with activated dioxygen.
Reactions of (T MPP)M(C0)3 with 02 proceed to give an insoluble material
with no carbonyl ligands along with a soluble species that exhibits complex
v(CO) patterns that are dependent on reaction times. In addition,
(TMPP)M(C0)5 was detected as an intermediate in the soluble portion by IR
spectroscopy. Phosphonium salts such as [I-I-TMPP]+ and [CH3-TMPP]+
are the only readily identified species as determined by 1H and 31P NMR
spectroscopies. IR spectroscopy failed to reveal any clear indication of
coordinated 02 or the possible presence of [C03]2' and TMPP=0, due to the
complicated pattern of all TMPP-containing species in the same region. IR
spectroscopic data for an authentic sample of TMPP=0 were examined in
order to ascertain whether TMPP=0 is formed in the oxygen chemistry, and
the results indicated that TMPP=0 was formed in at least one reaction, but

66

this is not a reproducible result. Single crystals of a colorless product were
obtained by slow diffusion of Et20 into a reaction solution where [’BU4N]+
was introduced for ion exchange with [CH3-TMPP]+; the compound was
determined to be [’Bu4N]4[M08026] by X-ray crystallography which results
from complete oxidation of a portion of the Mo starting material. It is not
known whether [M03026]4' is actually one of the products of the dioxygen
reactions or a decomposition product after slow reaction with air.

As mentioned earlier, oxygen transfer to phosphine ligands is quite
facile, (i. e., from M(TMPP) to M(0=TMPP) in this work), therefore we
carried out deliberate reactions of TMPP=0 with (toluene)Mo(C0)3 to
attempt synthesis of an authentic TMPP=0 product. A brown precipitate
and a yellow solution were obtained after recrystallization from THF and
Et20. A Nujol mull spectrum of the brown precipitate revealed two intense
carbonyl bands at 1912 and 1762 cm'l, which mimic the pattern known for
tricarbonyl metal complexes. Four carbonyl bands at 2063 (w), 1973 (w),
1924 (s), and 1842 (m) cm"1 were observed in a Nujol mull spectrum of a
solid obtained from the solution after the solvent was removed under
vacuum. These results are not in accord with the findings of the 02
reactions with (TMPP)Mo(CO)3, a finding that supports the conclusion that
simple TMPP=0 compounds are not being produced.

Solution IR spectroscopy was employed in an attempt to gain insight
into potential reaction pathways for the 02 chemistry. A THF solution of
(TMPP)Mo(CO)3 was purged with 02 gas for 5 min, which resulted in an
immediate color change from yellow to pale yellow and precipitation of a
green solid. The reaction solution was stirred under an 02 atmosphere for
another 15 h. Solution IR spectra measured before and after purging (Figure
2.12) revealed that a small amount of (TMPP)Mo(CO)4 was present in

 

(I) .
1

 

 

 

 

 

 

v(COQ L J
W
‘1 NCO)
I 1 T ' I I
2400 2200 211!) 18!” 16(1)
WAVENUMBERS

Figure 2.12. Solution IR spectra of (T MPP)M0(C0)3 and 02 at various

reaction times.

68

solution along with (TMPP)Mo(CO)3 before the introduction of 02 as
shown in (a). After purging with 02 gas for 5 min, (T MPP)Mo(C0)5 as
well as free C02 gas were detected as shown in Figure 2.12(b). Formation
of C02 from reactions of 02 with metal carbonyls have been previously
reported,3j most often from the condensation of an intermediate containing a
four-membered ring metallacycle of M-C(0)-0-0. (TMPP)Mo(CO)5, free
C02, and a new broad feature band at ca. 1720 cm-1 were detected after 2 h
as shown in Figure 2.12(c). Frequencies of v(C0) for [C03]2‘ and C02
ligands differ greatly for various C02 complexes, thus it is not a simple
matter to assign structures based on v(CO) stretches of C02.5 The broad
feature may be a carbonate ligand, or an intermediate that contains 112-C02.
The latter hypothesis is supported by a recent result obtained by Nicolas and
coworkerslk, who successfully characterized a 112-C02 metal complex, (11 5-
C5H4CH3)2Nb(n2-C02)CH2Ph, from the reaction of (115-
C5H4CH3)2Nb(CO)CH2Ph with air or 02. With continuous stirring under
an 02 atmosphere, solutions of (TMPP)Mo(CO)3 produce
(TMPP)Mo(CO)5, C02, and two weak bands between 1700 -1800 cm'1 after
15 h as indicated in Figure 2.12(d).
E. Carbon Dioxide Reactions of (TMPP)M(C0)3 ( M = M0, 1; W, 4).
The first structurally characterized C02 adduct was discovered by
Aresta and Nobile from reactions of coordinatively unsaturated zero-valent
Ni(PCy3)3 or [(Ni(PCy3)2)2N2] (PCy3 = tricyclohexyl phosphine) with C02
in toluene at room temperature; the C02 ligand was found to be bound to the
Ni atom in an n2 mode.1a One year later, Herskovitz and Guggenberger
discovered a second type of C02 adduct in the compound
IrCl(C204)(PMe3)2, in which two C02 molecules were found to be
dimerized and involved in a metallacycle with the Ir atom.lb These two

69

early examples illustrate the usefulness of highly basic transition metals (late
transition metals) for the fixation and further activation of C02. It was later
demonstrated that early transition metal complexes also react with C02 to
promote deoxygenation and disproportionation of C02. The proposed
mechanism proceeds through a preliminary fixation of C02 followed by
head-to-tail dimerization, and finally ending with carbon-oxygen bond
cleavage.1d In other work, Floriani and co-workers explored a useful
strategy for C02 fixation by combining a Lewis acid metal (alkali metal ion)
and a basic, low-valent late transition metal.1f With this combination, a C02
molecule can bond through an oxygen atom to the Lewis acid metal and
through the electron-deficient carbon to the basic metal at the same time as

shown below.

 

M = Li, Na, K; L = THF; 011-162) = salen-type ligand as shown below

CC. .53

RC——CR

-2

The zero-valent complexes (TMPP)M(C0)3, that contain a highly

basic, flexible TMPP ligand, could lead to a number of events as mentioned

70

above. Reactions of (nZ-TMPP)M0(C0)4 with C02 result in the formation
of (TMPP)Mo(CO)5 and an unknown species with no carbonyl vibrations
except for a weak feature appearing at 1929 cm]. (T MPP)Mo(C0)5 is
considered to be one of the products obtained from the disproportionation of
C02, while the C032' moiety may remain in its free ion form or may react
with another portion of (T MPP)M0(C0)4 to form a product without
carbonyl ligands. Unfortunately, (T MPP)Mo(C0)5 and the phosphonium
salts [H-TMPPP and [CH3-TMPP]+ were the only species detected by NMR
spectroscopy.

Due to our inability to isolate a C02 adduct from the above reaction,
the strategy used by Floriani in C02 fixation, namely the addition of NaPF6
01' KB F4 was attempted with reactions of (TMPP)M(C0)3 (M = M0, W) in
the Presence of C02 to attempt the stabilization of a metal-bound C02
ligand- (TMPP)M(C0)4 and a carbonyl-deficient species possessing only a
weak IR band at ca. 1930 cm‘1 were obtained from reactions carried out in
the presence of N aPF5 or KBF4, and it was noted that the reaction proceeded
more Slowly when N a+ or K+ ions are present.

In conclusion, disproportionation of C02 was observed from the
reacti<>ns of (TMPP)M(C0)3 and C02, most likely through preliminary
fixation and head-to-tail dimerization as proposed by C00per, where a CO
“10139 llle is transferred to the metal center to form (TMPP)M(C0)4. The
1lesultillg C032‘ moiety may remain in its free ion form or react with another

equivzilent of (T MPP)Mo(C0)4 to form a product without carbonyl
ligandsjh
F‘ Sulfur Dioxide Reactions of (TMPP)M(C0)3 (M = M0, 1; W, 4).

There are three basic bonding modes of 802 to metal centers as shown

on he)“ page.5b

71

906

§ ’12») M Q “°6
5 “0% O ©§O “alien

nl—planar 111—pyramidal 112-side on

 

 

 

The 802 molecule is capable of acting as a Lewis base to form an 111-planar
complex or as a Lewis acid to form an 111-pyramidal complex. The
molecule can also act as a ir-acid to form an n2 complex. A series of
molybdenum and tungsten 802 complexes with carbonyl and nitrogen donor
ligands have been structurally characterized in either 111-planar or n2
geometries. The v(S-O) stretch is a useful tool for structural analysis in the
absence of X-ray studies.5 No 802 insertion reactions have been observed
for group VI transition metal complexes, but a few examples of Group VI
complexes with bridging 802 ligands have been fully characterized.5 The
reaction of (ql-TMPP)M(C0)3 (M = M0, W) with 802 resulted in an
imilled iate color change from yellow to amber. The reaction is exothermic
and is also irreversible as judged by IR spectroscopy. Two new IR bands at
1338. and 1325 cm“1 (which are assigned to v(80)), were detected in the
THF leaction solution by IR spectroscopy after 3 min. After separation and
Purification, the acetone solution IR spectrum exhibited a v(SO) band at
1134 as well as two new v(CO) bands at 1974 and 1911 can-1 when M = w.
For the corresponding molybdenum complex, the v(S0) band appeared at
1133 cm-1 , while two v(CO) bands were observed to occur at 1980 and
1919 Cm'l. Unfortunately, Nujol mull spectra of both products could not

be used to predict the coordination geometry from examples in the

72

literature,5 due to the complicated fingerprint region of the TMPP ligand
which overlaps with the v(S-O) region. However, an increase in the C-0
stretching frequency suggests that metal to carbonyl backbonding decreases
as a result of the S02 ligand acting as an electron acceptor in an n1-
pyramidal or n2 mode. Attempts to characterize S02 containing products
under various reaction conditions, (e. g. lower temperatures, various solvents
(acetone, THF, benzene, toluene), NMR solution reaction, and various

reaction times) met with little success. Only the phosphonium salts [H-

"FL/[PP]+ and [CH3—TMPP]+ were detected by 1H and 31P NMR

spectroscopies. In conclusion, reactions of (TMPP)M(C0)3 with 802

aPpear to form complexes wherein the 802 ligand is bound in an n1-

pyramidal or n2 mode, but the products are very unstable and further

decompose to intractable compounds and phosphonium salts.

G. Summary

The chemistry of group VI tricarbonyl compounds with tertiary
Phosphine ligands has produced some unusual compounds, most notably the
5131: examples of molecular hydrogen complexes M(C0)3(PR3)2(H2) (M =
M0: W ; R = l'Pr, cy).4 The chemistry described here differs remarkably from
that observed for these systems. The most significant difference is the
PhOSphine stoichiometry; the parent compound in this study namely
M(C())3(TMPP) exists as a mono-phosphine species owing to the presence

9f Pendent methoxy groups that participate in reversible binding to the
mmSition metal and stabilize the coordinative unsaturation. The reactions of
(TMPP) M(C0)3 with small molecules were undertaken to explore the
flexibility of the ligand TMPP, which can bind in n1, n2, and n3 bonding
mOdeS as described above. Indeed, the results of the C0 studies nicely

Illustrate the concept of reversible coordination of ether substituents.

73

A second major difference from the previous research in bulky
phosphine compounds of Group VI metals is that the reactions of (113-
TMPP)M0(C0)3 with molecular hydrogen or nitrogen proceed with C0
displacement rather than by the formation of adducts. By employing the
flexible ether-phosphine ligand TMPP, we were able to isolate (n2-

TMPP)Mo(C0)4 and (nl-TMPP)M0(C0)5 from the reactions of (113-
TMPP)Mo(C0)3 with C0 (Scheme 1). As the equations clearly depict,
chemistry involving (nZ-TMPP)M0(C0)4 and (nl-TMPP)M0(C0)5 is
reversible whereas the reaction to produce (112-TMPP)M0(C0)4 from (113-
TM PP)Mo(C0)3 is irreversible. The same trend is observed in the reactions
0f (n3-TMPP)Cr(C0)3 with C0, while the chemistry involving (112-
TM PP)W(C0)4 and (111-TMPP)W(C0)5 is irreversible.
In conclusion, it has been demonstrated that TMPP can adopt a variety
0f coordination modes depending on the demands of the metal center.
Electron accepting and/or less sterically hindered ligands are more
compatible with this system due to the bulky, highly basic nature of TMPP
ligand coupled with electron-rich zero valent metal centers. This conclusion
is Supported by the reactions with acetylenes possessing electron-
Withdrawing substituents. Dissociation of the bonded TMPP ligand,
followed by methylation was observed in the reactions of (TMPP)M(C0)3
(M = M0, W) with PhCE-CH, while the formation of a stable adduct was
observed in the reaction with Me02CCECC02Me. Failure to isolate 802,
C02 and 02 adducts can be attributed to the instability of the molecules and

to the overall complexity of these reactions.

74

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17.

18-

19-

20-

21.

77

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(a) Comprehensive Organometallic Chemistry; Wilkinson, S. G.;
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1987, 109, 1401 and references therein.

 

CHAPTER III

COORDINATION CHEMISTRY OF TRIS(2,4,6-
TRIMETHOXYPHENYL)PHOSPHINE WITH LATE
TRANSITION METALS

78

79

1. Introduction
There has been considerable interest in the subject of the
coordination of functionalized (P,0) ligands to transition metal complexes.
Ether functionalized ligands are of special interest because weak metal-
ether interactions have been correlated with increased reactivity at the
metal center.1'2 This has been demonstrated, for example, in the
selectivity enhancement of the Ni(II) catalyzed oligomerization of ethene.3
The chemistry of low-valent Co(I,II) complexes with hemilabile (P,0)
1i gands is also very important due to the role the complexes play in
methanol carbonylation catalysis.4 The chemistry of these ligands has been
recently detailed in a review by Lindner et al..5 Unusual features of the
ether-phosphine molecule tris(2,4,6-trimethoxyphenyl)phosphine, (TMPP),
under investigation in our laboratories are its high basicity and the
Presence of multiple ether substituents that participate in various bonding
InC>Ci<es (n1 to n3, and monometallic to tetrametallic) as mentioned in

Chapter 2.

Pd(II) complexes typically exhibit square-planar geometries,
al':lj()l1.gh five coordinate species are occasionally encountered.6 Two
examples of octahedral Pd(II) complexes were reported in 1968 and 1973.7
The use of polydentate ligands with special geometric requirements to
favor octahedral coordination of Pd(II) has met with success in recent
years , e.g. pseudo-octahedral Pd(II) complexes with crown thioether
ligand 8 are known to adopt conformations with four short Pd-S bonds and
two long Pd-S contacts.3'13

A considerable body of research involving Ni(III) coordination
Chem is d the biolo ical im ortance of com ounds with
8111f“ try centers aroun . g p - p . .

r and sulfur/mtrogen ligands as models for the active srtes of N1

8O

enzymes.14‘19 In spite of much research in this area, structurally
characterized pairs of Ni(II)/Ni(III) compounds with identical ligand sets
have rarely been encountered.”19 It is relevance to expand the arena of
Ni(II)/Ni(III) chemistry with a variety 0f multidentate ligands including
(P,O) ligands that can stabilize unusual geometries.

Cadmium is known, like zinc, to play an important role in the
coordination chemistry of metalloenzymes bonding through sulfur,
nitrogen, and oxygen. A replacement of divalent zinc by divalent cadmium

in metalloenzymes decreases but does not destroy the enzymatic activity.20
Through the use of (P,0) ligands, we synthesized divalent cadmium
complexes and studied the coordination chemistry.

As mentioned above, phosphino—polyether ligands have received
attention due to their application in homogeneous catalysis-"4,431
Complexes of Pt(II) and Co(I,II,III) containing (P,0) ligands fall into this
category, but only few examples exist in the literature.4a5,22 Herein we
fepOr-t the syntheses, X-ray structures, and spectroscopic data for a series
Of late tranisition metal complexes supported by two flexible ether-

phosphine ligands that are free to adopt an n2 or n1 mode of binding in a

Square-planar molecule,23,24b or n3 to give a distorted six-coordinate

00111130me
2 .

A-

Experimental Section

Physical measurements

Infrared spectra were recorded on a Nicolet 740 FT -IR

:Eh‘ophotometer. 1H NMR spectra were measured on Varian 300- or

resi QMHZ spectrometers; chemical shifts were referenced relative to the

aCetQI-lal proton impurities of acetone-d6 (2.04 ppm with respect to TMS),
I1itrile-d3 (1.93 ppm with respect to TMS) or chloroform-d1 (7.24

 

81

ppm with respect to TMS). 31P{1H} NMR spectra were obtained on a
Varian 300—MHz spectrometer operating at 121.4 MHz and were
referenced relative to an external standard of 85% phosphoric acid.
Elemental analyses were performed at Galbraith Laboratories, Inc.,
Knoxville, TN, or Desert Analytics, Tucson, AZ. Electrochemical
measurements were performed by using an EG&G Applied Research
Model 362 scanning potentiostat in conjunction with a BAS Model RXY
recorder. Cyclic voltammetry experiments were carried out at 22 :l: 2 °C

using 0.1M tetra-n-butylammonium hexafluorophosphate (TBAPF6) as a

supporting electrolyte. Ep,a and EPA: were referenced to a Ag/AgCl

electrode and uncorrected for junction potentials.

B - Synthesis
The starting materials Cd(N03)2-4(HzO) and CdC12-2.5(H20) were

Purchased from Fisher Chemicals, Inc., while PtC12(NCC6H5)2, szCo,
and Pd sponge were purchased from Strem Chemicals, Inc.; all were used
as received. Tris(2,4,6-trimethoxyphenyl)phosphine (T MPP) was prepared
according to published methods25 or purchased from Aldrich and used
Without further purification. [M(NCCH3)n][BF4]2 (M = Fe, Co, Ni, 11 =
6;26a M = pd,26b pt,26c n = 4), and [szFe][BF4] 26d salts were prepared as
deseribed in the literature. Acetone was distilled over 3 A molecular
sleVeS, whereas methanol (MeOH) was distilled over Mg(0Me)2 under a
nitrogen atmosphere. Benzene, diethyl ether (Et20), tetrahydrofuran
(THF) , and toluene were distilled over sodium-potassium/benzophenone,
Whereas methylene chloride was distilled over P205 under a nitrogen
atLliQSI>here Unless otherwise specified, all reactions were carried out

uncle
r an argon atmosphere by using standard Schlenk-line techniques.

82

(1) Preparation of CoII(TMPP-0)2 (12).
A mixture of [Co(NCCH3)6][BF4]2 (0.200 g, 0.418 mmol) and
TMPP (0.890 g, 1.671 mmol) in a molar ratio of 1:4 in acetone was stirred
under argon for 12 h at r. t. to yield a dark green solution. The volume of
the resulting solution was reduced under vacuum and THF was added to
precipitate a white solid identified as [CH3-TMPP][BF4]. The same
procedure was repeated several times until no further traces of [CH3-
TMPP][BF4] salt were detected in the soluble portion as judged by 1H NMR
spectroscopy. Recrystallization of the soluble portion from acetone and
diethyl ether yielded a dark green compound CoH(TMPP-0)2 (1 2) in 45%
yield (0.206 g). X-ray quality dark green single crystals were grown by
slow diffusion of diethyl ether into an acetone solution of the title
compound.

(2 ) Preparation of [CoIIKTMPP-0)2][BF4] (13).

CoH(TMPP-0)2 (0.100 g, 0.091 mmol) was treated with one
equivalent of [szFe][BF4] (0.025 g, 0.091 mmol) in acetone at r. t. for 1
1’, afier which time the solvent was removed by vacuum distillation. The
crude product was washed with diethyl ether (10 mL x 4) to remove the

soluble szFe by-product. 'Ihe olive green compound [CoIHCI‘MPP-
0)2] [BF4] (13) was obtained in 81% yield (0.087 g). 1H NMR (8 in
acetOneaé): -0Me: 3.03 (s, 6H), 3.32 (s, 6H), 3.50 (s, 6H), 3.60 (s, 6H),
3'62 (S, 6H), 3.86 (s, 6H), 3.92 (s, 6H), 4.18 (s, 6H); meta-H: 5.44 (d, 2H),
(53:9 (d, 2H), 5.79 (d, 2H), 5.96 (d, 2H), 6.31 (s, br, 2H), 6.91 (d, 2H).
Preparation of Nill(TMPP-0)2 (14).

A mixture of [Ni(NCCH3)6][BF4]2 (0.200 g, 0.418 mmol) and TMPP

(0.8 90 1 672 mmol) in a molar ratio of 1:4 in THF was stirred under
g, .

"th for 12 h at r. t. and then filtered to remove a white solid identified

 

83

as [CH3-TMPP][BF4]. Recrystallization of the filtrate residue (which was
obtained after evacuation of the filtrate to dryness in vacuo) from THF and
diethyl ether gave the orange-brown compound NiH(TMPP-0)2 (14) in
51% yield (0.234 g). 1H NMR for 14(5, acetone-d6, -80 °C): -OMe: 2.98
(s, 6H), 3.24 (s, 6H), 3.29 (s, 6H), 3.40 (s, 6H), 3.49 (s, 6H), 3.68 (s, 6H),
3.73 (s, 6H), 4.10 (s, 6H); meta-H: 5.21 (br, s, 2H), 5.27 (br, s, 2H), 5.47
(br, s, 2H), 5.78 (br, s, 2H), 5.87 (br, s, 2H), 6.33 (br, s, 2H). Anal. Calcd
for 14, NiP2013C52H60: C, 57.11; H, 5.53. Found: C, 56.92; H, 5.68.
Cyclic voltammetry in CHzClz at a Pt disk electrode vs a Ag/AgCl
reference: (El/2)” = - 0.07 V vs Ag/AgCl.
( 4) Preparation of [NiIIKTMPP-0)2][BF4] (15).

NiH(TMPP—0)2 (0.085g, 0.077 mmol) was treated with one
equivalent of [CpQFe][BF4] (0.021 g, 0.077 mmol) in acetone at r. t. for 1
h, afler which time the solvent was removed by evaporation under vacuum.
The crude product was washed with diethyl ether to remove szFe, then
dried under vacuum to yield the dark green compound [Nim(TMPP-

0)2] 1:31:41 (15) in 71% yield (0.065 g). Anal. Calcd for 15,
Ni P2013C52H603F4: c, 52.91; H, 5.12. Found, c, 52.54; H, 5.20.
(5') Preparation of [Pd(TMPP)2][BF4]2 (16).
An acetone solution containing two equivalents of TMPP (0.476 g,
0900 mmol) was added dropwise to an acetone solution of
FPdCNCCH3)4][BF4]2 (0.200 g, 0.450 mmol) at -44 °C which effected an
Immediate color change from pale yellow to red. The resulting solution
was Stirred for 40 min at -44 °C and evaporated to dryness in vacuo. The
Sir::0und was recrystallized from acetone and diethyl ether to give a
‘red solid in 82 % yield (0.993 g). 1H NMR (6 in acetone-d6,

‘80 t)
C): -0Me: 3.32 (s, 6H), 3.34 (s, 6H), 3.47 (s, 6H), 3.52 (s, 6H), 3.83

84

(br, 18H), 4.03 (s, 6H), 4.25 (s, 6H); meta-H: 5.70 (br, 2H), 5.92 (br, 2H),
6.19 (br, 2H), 6.30 (br, 2H), 6.43 (br, 2H), 6.78 (br, 2H). 31P NMR (6 in
acetone-d6), +1.67. Anal. Calcd for 16, PdP2C54O13H66B2F3: C, 48.22;
H, 4.95. Found: C, 48.29; H, 5.05. UV-Vis (CH2C12): Amax (nm) (8 (
M‘1,cm’1)) 485 (2.3x104), 373 (3.7x104), 260 (1.7x105). Cyclic
voltammetry in CHzClz at a Pt disk electrode vs a Ag/AgCl reference:
Ep,c(1) = -1.03 V, Ep,a(1) = -0.90 V, Ep,c(2) = -0.75 V, Ep,a(2) = -0.56 V,

Ep,a(3) = +0.90 V VS Ag/AgCl.
( 6) Preparation of Pd(TMPP-0)2 (17).

An acetone solution containing four equivalents of TMPP (0.719 g,

1 -352 mmol) was added dropwise to an acetone solution of

[Pd(NCCH3)4][BF4]2 (0.150 g, 0.338 mol) at 0 °C which resulted in an

immediate color change from pale yellow to orange. The resulting

solution was stirred for 2 h at 0 °C, then warmed to r. t. and stirred for an
additional 12 h. The solvent was removed by evaporation under vacuum to
yield an orange solid. This solid was recrystallized from THF and diethyl
ether, then washed with a mixture of hexanes and acetone (v/v 2/3) to
re'31<)\Ie trace amounts of [CH3-TMPP][BF4] to give an orange compound in
78 % yield (0.301 g). 1H NMR (6 in chloroform-d1): -0Me: 3.10 (s, 6H),
3' l 2 (s, 24H), 3.66 (s, 6H), 3.75 (s, 12H); meta-H: 5.34 (br, 2H), 5.80 (br,
83) ’ 6- 13 (br, 2H). 31P NMR (5 in chloroform-d1), -3.07.
‘7) Preparation of [Pt(NCCH3)2(TMPP)2][BF4]2 (18).
A CH3CN solution containing two equivalents of TMPP (0.240 g,
0.430 mmol) was added dr0pwise to a CH3CN solution of
[Pt(NCCH3)4][BF4]2 (0.120 g, 0.225 mmol) at 0 °C. The resulting solution
;:: Stirred for 40 min at 0 °C and the solvent was removed in vacuo to
a pale yellow solid. The solid was recrystallized from CH2C12 and

85

Et20 to give a pale yellow solid in 73% yield (0.250 g). 1H NMR (5 in

acetonitrile-d3): 3.33 (s, 6H, CH3CN); -0Me: 3.42 (br, 12H), 3.61 (br,
24H), 3.78 (s, 6H), 4.82 (s, 12H); meta-H: 6.11 (t, 4H), 6.15 (d, 8H). 31P
NMR (5 in acetonitrile-d3), 445. Anal. Calcd for 18,
PtP2C53013H72NszF3: C, 45.96; H, 4.79. Found: C, 43.14; H, 4.50.
This high degree of error is attributed to the usual problems encountered

with the elemental analyses of acetonitrile complexes.

(8) Preparation of Pt(TMPP-0)2 (19).
(i) Reaction of PtCl2(NCC5H5)2 with 2 equiv. of TMPP.

An acetone solution containing two equivalents of TMPP (0.338 g, 0.636
mmol) was added dropwise to an acetone solution of PtC12(NCC6H5)2
(O- 1 50 g, 0.318 mmol) at 0 °C. The resulting solution was stirred for 12 h
under reduced pressure to remove the MeCl(g) by-product after which time
the solvent was removed by vacuum distillation to give a pale yellow solid,

which was recrystallized from acetone and Et20, washed with Et20, and

final] y dried under vacuum to yield a pale yellow compound. 1H and 31F
N M R data for the compound revealed a mixture of Pt(TMPP-0)2,
”5C 1 (TMPPXTMPP-O), and the methyl-phosphonium salt [CH3-TMPP]+.
X~Iay quality single crystals of PtCTMPP—0)2 were obtained from a

801 l—ltion of the compound in EtCN and Et20 at 0 °C.
(ii) Reactions of [Pt(NCCH3)4][BF4]2 with 4 equiv. of

T
M PP. An acetone solution containing four equivalents of TMPP (0.600
g, 1 - l 26 mmol) was added dropwise to an acetone solution of

[Pt(NCCH3)4][BF4]2 (0.150 g, 0.281 mmol) at 0 °C. The resulting solution
Wa
S Stirred for 12 h after which time the solvent was removed by

CVa
TH E Oration to give a pale yellow solid. The solid was recrystallized from
and Et20 to give a pale yellow solid, which was dissolved in a

86

mixture of THF and Et20 and filtered through Celite to remove the
insoluble methyl phosphonium salt, [CH3-TMPP][BF4]. The volume of the
filtrate was reduced under vacuum to give a yellow residue, which was
washed with Et20 and dried under vacuum to yield a pale yellow
compound in 58% yield (0.201 g). 1H NMR (5 in acetonitrile-d3,), -OMe:
3-40 (s, 6H), 3.58 (s, 24H), 3.69 (s, 6H), 3.82 (s, 12H); meta—H: 5.58 (q,
2H), 5.81 (q, 2H), 6.15 (d, 8H). 31P NMR (5 in acetonitrile-d3), -24.9 (s,
Ithp = 1950 Hz). Anal. Calcd for 19, PthC54O13H6632Fg: C, 50.61; H,

4-90- Found: C, 49.57; H, 5.05.

(9) Preparation of PtCl(TMPP)(TMPP-0) (20).

A mixture of PtC12(NCC6H5) (0.150 g, 0.318 mmol) and TMPP
(0-338 g, 0.636 mmol) were loaded in a Schlenk flask, dissolved in 30 mL
of 'I‘IIF and stirred for 2 days under reduced pressure to remove the
M eCl(g) by—product. A pale yellow precipitate and a yellow solution were
obtained. The precipitate was discarded, the yellow solution was filtered

into a second flask, and the volume of the filtrate was reduced under

Vac uum, Et20 was then added to precipitate a pale yellow solid, which was

Washed with a mixture of acetone and Et20 to remove trace quantities of

[ms—TMPW, washed with Et20 and finally dried under vacuum to yield

a p ale yellow compound in 40 % yield (0.163 g). IR (Nujol, cm‘l) v(PtCl)

326- 1H NMR (5 in acetonitrile-d3), -0Me: 3.28 (s, 3H), 3.38 (s, 30H),

3'5 8 (s, 3H), 3.75 (s, 9H), 3.77 (br, 6H); meta-H: 5.29 (m, 1H), 5.38 (m,

(1:)? S -99 (d, 6H), 6.04 (d, 4H).

Preparation of Cd(N03)2(TMPP) (21)
A mixture of Cd(N03)2-4(HzO) (0.100 g, 0.324 mmol) and TMPP

(O- 7
of 1 3 g, 0.324 mmol) were loaded in a Schlenk flask, dissolved in 15 mL
:eOH and stirred overnight. The resulting colorless solution was dried

 

 

87

under vacuum to give a white solid. The solid was redissolved in CH2C12,
and Et20 was added to precipitate a white solid, which was washed with
Et20 and dried in vacuo to yield a white compound (0.201 g, 81% yield).
1H NMR (5 in acetone-d6), -OMe, 3.42 (s,l8H), 3.59 (s, 18H), 3.84 (s,
18H); meta-H, 6.15 (br, 6H), 6.23 (d, 6H).

(11) Preparation of CdC12(TMPP)2 (22)
A mixture of CdC12-2.5(H20) (0.100 g, 0.438 mmol) and TMPP
(0.466 g, 0.876 mmol) was dissolved in 20 mL of MeOH, and stirred for
12 h under reduced pressure to remove the MeCl(g) by-product. A
colorless solution and a white precipitate were obtained. The former was
removed via cannula techniques, while the latter was dried under vacuum
to give a white solid. The solid was washed with acetone (10 mL x 2) to
remove trace amounts of [CH3-TMPP]+, washed with Et20 and dried
under vacuum to yield a white compound. IR (Nujol, cm'l) v(CdCl) 258,
242- 1H NMR (5 in chloroform-d1), -OMe: 3.59 (s, ortho, 36H), 3.76 (s,
ma, 18H); meta-H: 6.07 (d, 12H). 31? NMR (5 in chloroform-d1), -66.6

(S, 1 Jan) = 1394 and 1460 Hz for 111Cd and 113Cd respectively).
(12) Preparation of [Cd(TMPP)2][BF4]2 (23)

An acetone solution of TMPP (0.518 g, 0.972 mmol) was added
“OW-1 y to a MeOH solution of Cd(N03)2.4(H20) (0.150 g, 0.486 mmol)
and tlle resulting solution was stirred for 1 h. A MeOH solution of NaBF4
(0‘ 1 0'7 g, 0.972 mmol) was added to the resulting solution and the reaction
2:111 ti on was stirred for 12 h. The volume of the solution was reduced
da 1‘ vacuum, and Et20 was added to precipitate a white solid which was
washed with Et20 and dried in vacuo. The solid was redissolved in acetone
and filtered through Celite to remove NaNO3. The volume of the filtrate
Wag reduced under vacuum and Et20 was added to precipitate a white

88

solid, which was washed with Et20 and dried under vacuum to give a white
compound in 83% yield. 1H NMR (5 in acetone-d6), -OMe: 3.48 (s, ortho,
36H), 3.86 (3, para, 18H); meta-H: 6.23 (t, 12H). 31P NMR (5 in acetone—
d6), 6.76 (s, 1JCdp = 1394 and 1460 Hz for 111Cd and 113Cd respectively).
C. X-ray Crystallographic Studies
Crystallographic data for compounds 1 2, 1 5, 1 6, l 8, 1 9, 2 l and 23
were collected on a Rigaku AFC6S diffractometer, while the data for 15
and 1 7 were collected on a N icolet P3N diffractometer; both are equipped
with monochromated Mo Ka radiation. A 2 KW sealed tube generator was
used for Rigaku data and a 3 KW sealed tube generator was employed for
N icolet data. Crystallographic computing was performed on a
VAXSTATION 4000 by using the Texsan crystallographic software
package of Molecular Structure Corporation.27 Crystal parameters and
basic information pertaining to data collection and structure refinement are
Summarized in Tables 3.1 (15), 3.3 (16 and 17), 3.5 (18 and 1 9), and 3.8
(2 1 and 23).
(l) Con(TMPP-0)2 (12). Single crystals of 1 2 were grown by a slow
diffilsion of hexanes into an acetone solution of the title compound. A dark
green crystal was secured on the tip of a glass fiber with Dow Corning
Silicone grease and placed in a cold N2(g) stream at -100 :l: 1 °C. Least-
Squares refinement using 16 well-centered reflections in the range 4.07 S
28 S 393° indicated that the crystal belonged to the monoclinic C-centered
Cwstal system with cell parameters a = 21.088 (7) A, b = 25.056 (12) A, c
F 26 -366 (11) A, 0 = 112.14 (3) °, v = 12904 (10) A3, and z = 8. Data
cc>lleQtion was abandoned due to a decay of the crystal attributed to rapid
SDI v Qlint loss.

89

(2) [NiIII(TMPP-0)2][BF 4] (15). Single crystals of 15 were grown

by a slow diffusion of hexanes into an acetone solution of the title

compound. A dark green crystal of dimensions 0.34 x 0.78 x 0.39 mm3

was secured on the tip of a glass fiber with Dow Corning silicone grease

and placed in a cold N2(g) stream. Least-squares refinement using 24 well-

centered reflections in the range 15.41 S. 20 S 24.38° indicated a triclinic

crystal system. The data were collected at - 85 i 1 °C using the w-20 scan

technique to a maximum 20 value of 47°. Of the 9507 reflections that were

collected, 9006 were determined to be unique. The structure was solved by

direct methods in the space group P-l by using MITHRIL23, with

subsequent development in the DIRDIF29 program. An empirical

absorption correction was applied by using the program DIFABS after all

non-hydrogen atoms had refined isotropically to convergence.30 All non-

hydrogen atoms were refined anisotropically. The final full-matrix

1‘ efinement was based on 5102 observed reflections with F02> 30(F02) that

Were used to fit 735 parameters to give R = 0.069 and Rw = 0.068. The

goOdness-of-fit index was 2.60, and the highest peak in the final difference
map ‘was 1.04 e‘lA3.

(3) [Pd(TMPP)2][BF4]2 (16). Single crystals of 1 6 were grown by a
Slow diffusion of diethyl ether into a CH2C12 solution of compound 1 6. A
red C rystal of dimensions 0.49 x 0.36 x 0.40 mm3 was seemed on the tip of

331a 85 fiber with Dow Corning silicone grease and placed in a cold N2(g)
Strea 1:11. Least-squares refinement using 21 well-centered reflections in the
range—‘- 25.5 S 20 .<_ 34.6° indicated an orthorhombic crystal system. The
data \Jvere collected at - 110 i 1 °C using the w-20 scan technique to a
maxi Ilium 20 value of 47°. A total of 4837 reflections was collected, of
Which 4181 data with I > 0.010(1) were used for F? refinement, and 3298

90

data with I > 3.000(1) were used for F refinement. An empirical
absorption correction based on azimuthal scans of three reflections was
applied which resulted in transmission factors ranging from 0.92 to 1.00.
The data were corrected for Lorentz and polarization effects. The space
group was determined to be Pna21 based on the observed systematic
absences. The structure was solved by the MITHRIL program, followed
by DIRDIF structure solution programs and refined by full-matrix least-
squares refinement.23'29 The phenyl rings of the TMPP ligands were
refined isotropically for the F2 refinement and were treated as rigid groups
for the F refinement to reduce the number of parameters. F2 refinement
of 585 parameters resulted in residuals of R = 0.075 and Rw = 0.101,
while refinement on F of 433 parameters resulted in residuals of R = 0.057
and Rw = 0.074. Attempts to solve the structure in the higher symmetry
Space group Puma (#62) were unsuccessful. Both enantiomorphs of the
Honcentrosymmetric space group (#33) were refined, but no statistically
Significant difference in the residuals R and Rw (0.0751, 0.1009 and
0. 0750, 0.1009, respectively) were observed.

(‘0 Pd(TMPP—0)2 (17). Single crystals of 17 were grown by a slow
dflfilsion of diethyl ether into a CH2C12 solution of compound 1 7. An
Orange crystal of dimensions 0.40 x 0.98 x 0.22 mm3 was secured on the
tip 0 f a glass fiber with Dow Corning silicone grease and placed in a cold
. N2 (g) stream. Least-squares refinement using 25 well-centered reflections
In the range 15.0 S 20 5 223° indicated that the crystal belonged to an
3:119 Ihombic crystal system. The data were collected at - 85 i 1 °C using

(5) (‘0 ~20 scan technique to a maximum 20 value of 47°.
[Pt(NCCH3)2(TMPP)2][BF4]2 (18). Single crystals of 18 were
ngWh by a slow diffusion of diethyl ether into a solution of 1 8 in acetone

91

and CH2C12. A pale yellow crystal of dimensions 0.29 x 0.44 x 0.29 mm3

was secured on the tip of a glass fiber with Dow Corning silicone grease

and placed in a cold N2(g) stream. Least-squares refinement using 21 well-

centered reflections in the range 20.2 S 20 S 25.6° indicated a triclinic

crystal system. The data were collected at - 100 i 1 °C using the 00-20

scan technique to a maximum 20 value of 47°. Of the 9951 reflections that

were collected, 9519 were unique. An empirical absorption correction

based on azimuthal scans of three reflections was applied which resulted in

transmission factors ranging from 0.84 to 1.00. The data were corrected

for Lorentz and polarization effects. The structure was solved in the space

group P—l with the program PHASE?"1 followed by DIRDIF?9 structure

solution programs and refined by full-matrix least-squares refinement. All

non-hydrogen atoms were refined anisotropically. The final full-matrix

refinement was based on 7081 observed reflections with F02> 30(F02) that

Wer‘e used to fit 820 parameters to give R = 0.036 and Rw = 0.045. The

goodness—of-fit index was 1.64, and the highest peak in the final difference
map was 1.59 e‘lA3.

(6) Pt(TMPP-0)2'3EtCN (19}3EtCN. A pale yellow crystal of

dimensions 0.36 x 0.27 x 0.36 mm3 was secured on the tip of a glass fiber

with Dow Corning silicone grease and placed in a cold N2(g) stream.

Le‘Ei—S‘t-squares refinement using 21 well-centered reflections in the range

20’ 1 9 S 20 S 24.09° indicated that the crystal belonged to a monoclinic

Crystal system. The data were collected at -100 i 1 °C using the w-scan

tE:<:l:l‘~'lique to a maximum 20 value of 47°. Of the 9900 reflections that were

coll eeted, 9420 were unique. The data were corrected for Lorentz and

pO‘lq‘lfization effects and an empirical absorption correction based on

a22:112t1l1thal scans of three reflections was applied which resulted in

92

transmission factors ranging from 0.95 to 1.00. The space group was
determined to be P21/c based on the observed systematic absences. The
structure was solved and developed with the use of the MITHRIL and
DIRDIF structure solution programs and refined by full-matrix least-
squares refinement.23'29 All non-hydrogen atoms were refined
anisotropically, with the final cycle being based on 6082 observed
reflections with F02> 30(F02) that were used to fit 766 parameters to give
R = 0.042 and Rw = 0.047. The goodness-of-fit index was 1.39, and the

highest peak in the final difference map was 0.85 e‘lA3.
(7) Cd(N03)2(TMPP) (21). Single crystals of 21 were grown by a
slow diffusion of diethyl ether into a CHzClz solution of compound 2 1. A
colorless crystal of dimensions 0.26 x 0.39 x 0.23 mm3 was secured on the
tip of a glass fiber with Dow Corning silicone grease and placed in a cold
N2 (g) stream. Least-squares refinement using 17 well-centered reflections
in the range 31.60 S 20 S 39.21° indicated that the crystal belonged to an
orthorhombic crystal system. A total of 2798 reflections were collected at
‘1 00 i 1 °C using the 00-20 scan technique to a maximum 20 value of 47°.
The data were corrected for Lorentz and polarization effects and the space
gr 0 up was determined to be Pna21 (#33) based on the observed systematic
abse races. An empirical absorption correction, using the program DIFABS,
was applied which resulted in transmission factors ranging from 0.77 to
1‘00 ~ 30 The structure was solved and developed with the use of the
MITIHRIL and DIRDIF structure solution programs and refined by full-
Irlatrix least-squares refinement.28‘29 All non-hydrogen atoms were
:56:th anisotropically except for ring carbons (Cl-C18), which were
ted with isotr0pic thermal parameters. The final full-matrix
re1:?‘1nement was based on 1695 observed reflections with F02> 30(F02) that

93

were used to fit 273 parameters to give R = 0.049 (Rw = 0.063) and a
goodness-of-fit index of 1.99. The highest peak in the final difference map
was 0.59 e‘lA3. Both enantiomorphs of the noncentrosymmetric space
group (#33) were refined, but no significant difference in the residuals R
and Rw (0.0493, 0.0633 and 0.0486, 0.0630, respectively) were observed.
(8) [Cd(TMPP)2][BF4]2 (23). Single crystals of 23 were grown by a
slow diffusion of diethyl ether into a solution of 23 in acetone and CH2C12.
A colorless crystal of dimensions 0.31 x 0.40 x 0.45 mm3 was secured on
the tip of a glass fiber with Dow Corning silicone grease and placed in a
cold N2(g) stream. Least-squares refinement using 20 well-centered
reflections in the range 9.57 S 20 S 12.58° indicated that the crystal
belonged to a monoclinic crystal system. Data were collected at -100 i 1
°C using the (ta-scan technique to a maximum 20 value of 45°. The space
group was determined to be C2/c based on the observed systematic
absences. The structure was partially solved by PHASE31 and DIRDIF29
Strllcture solution programs. The atoms associated with the Cd
c()()1:‘<lination sphere were located as were one of the [BF4]" anions;
add i tional efforts are required to locate an additional one-half of a [BF4]'
ani On.
3’ Results and Discussion
A" Reactions of Co11 and TMPP.

(1) Syntheses. Compound 1 2 was obtained from the reaction of
[COCNCCH3)6][BF4]2 and four equivalents of TMPP in ~ 45% yield. The
low yield of Co(TMPP-0)2 (12) is due to the difficulty in separating it
from the ubiquitous [CH3-TMPP][BF4] by-product. The two extra
eqlli‘Valents of TMPP in this reaction act as nucleophiles that attack the
deg tl‘ophilic methyl groups of the coordinated ether-TMPP moieties,

94

leading to the more stable phosphine-phenoxide product. If the reaction is
carried out with only two equivalents of TMPP under the same conditions,
only [CH3—TMPP][BF4] and [H-TMPP][BF4] are isolated with the metal
compound being difficult to identify. Reactions involving chlorinated
solvents or chloride-containing starting materials produced only salts
analogous to [H-TMPP][MC14] or [H-TMPP]2[M2CI6] (M = Fe, Co).32

(2) Electrochemistry of 12. Cyclic voltammetric studies of

compound Co(TMPP-0)2 have been performed that reveal an oxidation at
+ 0.50 V (vs Ag/AgCl).33 Indeed, [CoCTMPP-0)2][BF4] (l 3) was obtained
from the chemical oxidation reaction of CoCTMPP—0)2 with [Cp2Fe][BF4]
as an olive-green compound.

(3) NMR Studies of 12 and 13. The 1H NMR spectrum of

Co(TMPP—0)2 reveals featureless resonances, which is expected for a
Paramagnetic d7 Co(II) compound. The room temperature 1H NMR
Spectrum of [Co(TMPP-0)2][BF4], however, consists of eight distinct
resonances for eight inequivalent ortho and para methoxy groups in the
range 3.0-4.2 ppm and six distinct resonances for six inequivalent meta
pro tons in the range 5.4-7.0 ppm. Consequently, the two TMPP-0 ligands
are bound to the Co(lII) atom in an n3 mode. As such, the ligands are not
”(De cted to participate in the fluxional behavior that is characteristic of 117-
°°° rdinated TMPP.

(4) Molecular Structures of 12. Data collection on crystals
0f Q C(TMPP-Oh (12) was thwarted due to a fast decay of the crystal
caused by solvent loss from the lattice. Attempts to grow crystals of the
:Elbound in various solvent combinations (such as THF/hexanes,

F/]5t20 and acetone/toluene) all failed. Crystal structures of the adducts
0f 1 2, MC12[C0(TMPP-0)2] (M = C0, Mn) were obtained from reactions

95

of 12 and divalent metal halides such as CoClz and MnClz. The structures
revealed a distorted square-planar geometry around Co atom with two
mutually cis-phosphorus atoms and two methoxy-oxygens that bridge to the

metal atoms of the divalent metal chlorides as depicted below.33

 

R
R\\ ’ ‘0 MC] R\\ ‘ ‘ C1
P\C / 2 P\ C / /
R/P/ °\0 , /P/ 0\o/ C]
R R
OMe
P R = C6H2(OMe)3
C _ MC12 = MnClz and COC12
O O OMe

These results suggest that compound 12 with unligated cis O-atoms
possesses a distorted square-planar geometry with a cis arrangement of P
and 0 atoms, but this cannot be definitely concluded due to the fact that
geometrical isomerization has been observed in Ni(ll)/(III) analogues,
Where the TMPP-0 ligands adopt different binding modes from cis in
Ni(II) to trans in Ni(III), as described in Section 8.220 Therefore, no

(“mansion can be drawn unless a complete crystal structure analysis of 1 2
can be attributed.

B- Reactions of Ni11 and TMPP.

(1) Syntheses. Compound 14 was obtained from the reaction of
[Ni(NCCH3)6][BF4]2 with four equivalents of TMPP in ~ 50% yield. The
low yield of 14 is due to the difficulty in separating the product from the
[CH3-TMPP][BF4] by-product. The two extra equivalents of TMPP in this

96

reaction act as nucleophiles that attack the electrophilic methyl groups of
the coordinated ether-TMPP moieties, thereby leading to a more stable
phosphino-phenoxide product. If the reaction is carried out with only two
equivalents of TMPP under the same conditions, only [CH3-TMPP][BF4]
and [Ii—TMPP][BF4] are isolated in large quantities. Reactions involving
chlorinated solvents or chloride-containing starting materials produced
only salts of the type [H-TMPP][MCI4] or [H-TMPP]2[M2C16] (M = Fe,
Co).32
(2) Electrochemistry of 14. Of considerable interest in this
work is the discovery that 14 exhibits a facile and reversible oxidation at
-0.07 V, the location of which suggested to us that a stable Ni(III) analog
should be accessible by chemical methods.5d Indeed, chemical oxidation
With ferrocenium proceeds smoothly to give a high yield of the d7 Ni(III)
analogue 1 5. The epr spectrum is typical of a d7 system possessing a dz2
ground state with an axial elongation in an octahedral field,10r34 with g
values of g_L = 2.28 and g// = 2.04 and a hyperfine coupling to the
phosphorus center (I = 1/2) of A// = 8 G. These results are in accord with
a Participation of the axial ether group in a bonding interaction with the
Niall) metal center.
(3) NMR Studies of 14 and 15. A 1H NMR spectrum of 14 at
room temperature revealed broad resonances which suggested that a
dynamic process was occurring in solution. Variable temperature 1H NMR
of 1 4 from +20 to -80 °C in acetone-d6 as shown in Figure 3.1 confirmed
the fluxionality of the ligand. The spectrum at -80° C contains eight
distinct resonances between 2.9 and 4.2 ppm due to the inequivalent ortho-
and para-methoxy groups and six resonances between 5.2 and 6.4 ppm
attlibuted to the meta protons. A 1H NMR spectrum of 1 5 at room

97

MA ”-80?
6-5 ::Q'""I.""r"v[rYT’Y—Y‘TTV‘I'V'IV§VI:

 

Figure 3.1. Variable temperature 1H NMR spectra of Ni(TMPP-0)2 (14) in
aCetone_d6.

98

temperature revealed featureless resonances, in agreement with its
paramagnetic d7 configuration as observed in epr spectroscopy.

(4) Molecular Structures of 14 and 15. Single crystal X-ray
crystallographic studies of [Ni(TMPP—0)2]0r+ as acetone solvates were
performed at low temperature. To our knowledge, these results represent
the first example of a structurally characterized Ni(II)/Ni(lll) pair
supported by an ether-phosphine ligand. An ORTEP drawing and selected
bond distances and bond angles for 15 are given in Figure 3.2 and Table
3.2, respectively. Compound 15 exhibits a distorted octahedral geometry,
with two mutually cis phosphorus and two phenoxide oxygen atoms in the
equatorial plane and two methoxy oxygen atoms in axial positions. The
average Ni-P bond distance in 15 is ~0.01 A shorter than that in 14. The
average N i-O(phenoxide) bond distance in 15 is 1.918 [5] A, whereas the
average Ni—O(ether methoxy) axial interaction is 2.193 [6] A. The axial
elongation is consistent with the results of the epr experiment and with the
expected trend for metal-ether distances versus metal-phenoxide bonds.
The rePorted range for Ni-O bonds in the octahedral Ni(II) compound
[Ni(O-CoHa(0H)CH=N-NHCSNH2)2]c12 is 2.09 - 2.14 A35 The angles P2—
Nil-OIS, Pl -Ni1-O4, O4-Ni1-OlS, and Pl-Nil-P2 range from 83.5 (2)°

to ““2 (1)° in the distorted equatorial plane. The isomerization of the
TMPP‘O ligand from cis to trans upon going from the d8 Ni(II) to the d7
.Ni(III) compound clearly reflects subtle electronic effects and not steric
n.lflllences, as it would be expected that trans geometries are less sterically
:mderod for bulky ligands than cis structures.
‘ ReaCtions of NH and TMPP.

(1) Syntheses. [Pd(TMPP)2][BF4]2 (1 6) was prepared from the

reaction of [Pd(NCCH3)4][BF4]2 with two equivalents of TMPP in acetone

Table 3.1. Summary of crystallographic data for
[Ni(TMPP-O)2][BF4}2(CH3)2CO (1 5-2(CH3)2CO).

 

 

1 5-2(CH3)2CO
formula NiP2020C58H7zBF4
formula wt 1296.65
space group 13.1
a, A 12.448 (4)

b, A 14.554 (6)
c, A 18.470 (6)
or, deg 73.33 (3)
5, deg 82.21 (3)
1. deg 71.16 (3)
Va A3 3031 (4)
Z 2

delacr g/cm3 1.421

f" Cm“ 4.55

temp: °C - 85 _+_ 1

Ra 0.069

wa 0.068

 

W
~ 2||Fo| 4 IFCIIIXIFOI. b 8., = [ZwlFoI - IFeI)2/2wlFol2]1’2;w =1/o7—0Fon.

100

 

Figure 32. ORTEP drawing of [Ni(TMPP—0)2][BF4] (15).

Table 3.2. Selected bond distances (A) and bond angles (deg) for

101

[Ni(TMPP-O)2][BF4]-2(CH3)2C0 (1 5-2(CH3)2CO).

Bond Distances

 

 

 

 

 

A B A-B (A)

Nil P1 2.222(3)

Nil 92 2.224(3)

Nil 01 2.189(1)

Nil 04 1.918(5)

Nil 010 2.196(6)

Nil 015 1.918 (5)

Bond Angles

A B C A-B-C (°)
P1 Nil P2 101.2 (1)
P1 Nil 04 83.9 (2)
P1 Nil 015 172.5 (2)
P2 Nil 015 83.5 (2)
P2 Nil 04 174.7(2)
01 Nil 010 177.0 (2)
O4 Nil 015 91.6 (2)

 

102

and isolated as a brick-red compound. This observation was immediately
noted as being unusual, as Pd(II) compounds are typically quite pale in
color.1321 Cyclic voltammetric studies of 16 were performed in 0.1 M
solution of ["Bu4N][PF6]/CH2C12 and revealed two irreversible reduction
waves at -0.75 V and -1.03 V vs Ag/AgCl as shown in Figure 3.3. The
first reduction at -0.75 V corresponds to the reduction of Pd(II) to Pd(I),
while the second irreversible reduction (at -1.03 V) involves a
decomposition of the molecule [Pd(TMPP)2][BF4]2. According to these
data, preparation of the d9 Pd(I) compound, [PdI(TMPP)2][BF4], should be
possible by chemical reduction of 1 6 with Con2.

In order to check the possibility of paramagnetism for this pseudo
six-coordinate complex, SQUID measurements were performed over the
range of 5 K to 300 K; under these conditions, the compound was
rigomusly diamagnetic. This is evidently a reflection of the orbital
Symmetry being sz as opposed to Oh. Future attempts to access a triplet
excited state by heating the sample above 300 K would be in order.

Preparation of the demethylated derivatives, M(TMPP-0)2 (M =

Co’ Ni, Rh) was achieved by employing two extra equivalents of TMPP to
act as a nucleophilic reagent as described above in Chapter 3 Sections A
and 3.33.22c,36 In order to avoid sacrificing TMPP molecules to prepare
the demethylated derivatives, Pd(TMPP-0)2 (l 7) was later synthesized
from reactions of [Pd(TMPP)2][BF4]2 (16) with various nucleophile
sources such as KI, LiNMez, and NaOMe. Unfortunately, all reactions
were not as Specific or complete as the one carried out with TMPP, with all
iozulting in mixtures of [CH3-TMPP][BF4], "[Pd(TMPP)(TMPP-0)][BF4]",
and 1 7, a conclusion that is supported by 1H and 31P NMR

Spe .
choseoI-‘files. As a result of these failed attempts, compound 17 was

103

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104

 

 

 

-10 ‘C

 

20°C

f

 

40‘C

 

«60'C

 

-70 °C

 

 

 

 

l l I 1 VI 1 l 1
111111T1 1111r111 11111111111111T1 11

SW4

Figure 3.4. Variable temperature 1H NMR spectra of [Pd(TMPP)2][BF4]2
(16) in acetone-d6.

105

finally obtained in best yields from the reaction of [Pd(NCCH3)4][BF4]2

with four equivalents of TMPP (75% yield as described in Section A and
B). The high yield of Pd(TMPP—0)2 (17) compared to the Co and Ni
analogues is due to the lower solubility of 17 in acetone, which renders it

more easily separated from the [CH3—TMPP][BF4] by-product. The
reactions of Pd(II) with TMPP are summarized as depicted below.

(2) NMR Studies of 16 and 17. Variable-temperature 1H
N MR studies of [Pd(TMPP)2][BF4]2 (1 6) in acetone-d6 from +20 to -80 °C
(Figure 3.4) indicate that the TMPP ligand is involved in a fluxional

process; such behavior has been noted for other (16 and (18 complexes of

 

 

 

 

“NM“? , ” [Pd(TMPP)2llBF412 (16)
KI [Pd(TMFPXTMPP-OflfBFd
[Pd(TMPP)2][BF4]2 r +
(16) NaOMe , Pd(TMEP-Oh (17)
2 TMPP k [CHs-TMPPHBF41
[Pd(NCCH3)4][BF4]2 M» Pd(TMPP-O)2 + 2 [CH3-TMPP][BF4]

(17)

Scheme 3.1 Reactions of Pd(II) with nucleophilic reagents and TMPP.

this ligand.22 The 1H NMR spectrum at -80 °C reveals six distinct
resonances between 5 = 5.60 - 6.80 ppm assigned to inequivalent meta
protons, six resonances between 5 = 3.30 - 4.25 ppm due to inequivalent
ortho-methoxy groups, and one broad resonance at 5 = 3.83 ppm due to
three para— methoxy substituents. This spectrum is consistent with
measured free rotation of the uncoordinated aryl group. A 31F N MR

106

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spectrum of 16 in acetone-d6 at room temperature exhibits a single
resonance at 5 = +1.67 ppm. These NMR data are in accord with the
presence of only one type of unsymmetrically coordinated phosphine ligand
and support a close relationship between the solution and solid-state
structures of the cation.

The room temperature 1H NMR spectrum of Pd(TMPP-0)2 (17)

(Figure 3.5) revealed four distinct resonances in the methoxy region of
TMPP-0 ligands between 3.0 and 3.8 ppm, which indicates that the
unbound rings on the TMPP ligands are involved in a free rotation (on the
NMR time scale) similar to that observed for the Ni(II) analogue.22c Two
of these four resonances are due to the inequivalent para (a) and ortho (b)
methyl groups of the bonded ring while the other two are due to four
equivalent ortho (c) and two equivalent para (d) methyl groups of the free
rings as depicted below. Three distinct resonances appear in the meta
proton region of TMPP-0 ligands between 5.3 and 6.2 ppm. Two of this
three resonances are due to two inequivalent meta protons (1 and 2) of the
bonded ring and the last one is due to four equivalent meta protons (3) of
the free rings as shown on the following page.
These NMR data are in accord with the presence of two types of
unsymmetrically coordinated rings of the tertiary phosphine ligand. A 31P
NMR spectrum of Pd(TMPP-0)2 (17) in chloroform-d1 at room
temperature exhibits a single resonance at 5 = -3.07 ppm as expected.

(3) Molecular Structures of 16 and 17. X-ray quality single
crystals of [PdH(TMPP)2][BF4]2 (1 6) were grown by slow diffusion of
diethyl ether into a CH2C12 solution of the compound. An ORTEP
drawing of the molecular cation as well as selected bond distances and

angles for 1 6 are provided in Figure 3.6 and Table 3.4. The Pd atom

108

 

H(3) H(3) OMe(d)
OMe(c)
(c)MeO H(3)
OMe(c)
OMe(b)
-. - H(2)
P\ /
Pd
/ \o OMe(a)
H(ly)

The other half of the molecule is omitted for clarity.

resides in the center of a pseudo-octahedron defined by two phosphorus
atoms (P1, P2), two ether-oxygen atoms (01, 010) in an equatorial
arrangement, and two ether oxygen atoms 04 and 013 in axial positions.
The distortion of the square-planar geometry around the Pd atom is easily
understood in terms of the requirements of the five-membered
metallacycles Pdl-Pl-Cl-CZ-Ol and Pdl-P2-C19-C20—OIO that involve
acute angles (Pl-Pdl-Ol = 78.3 (2)°, and P2-Pd1-010 = 78.1 (2)°). The
average Pd-Oaxia] distance of 2.651 A is the shortest axial contact reported
to date for a Pd(II) compound.14'20 In comparison, the corresponding
distances in PdHL6 complexes supported by trigonal (8,8,8) or (8,8,N)
ligands fall in the range 2.95-3.27 A.15'20

X-ray quality single crystals of Pd(TMPP—0)2 (1 7) were grown by
slow diffusion of diethyl ether into a CH2C12 solution of the compound. A
PLUTO drawing of the molecule 17 is provided in Figure 3.7. The Pd
atom resides in the center of a distorted square-planar environment defined

by two phosphorus atoms (P1, P2) and two methoxy-oxygen atoms (01,

109

Table 3.3. Summary of crystallographic data for [Pd(TMPP)2][BF4]2
(1 6) and Pd(TMPP—0)2-nCH2C12 (1 7-nCH2C12).

 

 

Compound 16 l7-nCH2C12
formula PdP2013C54H66BzF3 PdP2018C52H60
formula wt 1345.07

space group Pna21 Pbcn

a, A 20.71 (1) 20.162 (9)

b, A 17.838 (3) 24.33 (1)

0,15. 15.9008 (2) 25.62 (1)

01, deg 90 90

6, deg 90 90

Y, deg 90 90

v, A3 5876 (5) 12565 (10)

z 4 8

dclac, g/cm3 1.520

11, cm-1 4.56

temp,°C -110_+_1 -85:1

Ra 0.075

M 0.101

 

a R = leFol - IFcII/ZlFoI. b Rw = [ZWIFoI - ch|)2/ZWIF6|2]1’2; W = 1/02(|Fol)-

110

 

 

 

Figure 3.6. ORTEP drawing of [Pd(TMPP)2][BF4]2 (l6).

111

Table 3.4 Selected bond distances (A) and bond angles (°) for

[Pd(TMPP)2][BF4]2 (1 6).
Bond Distances

 

 

A B A-B (A) A B A-B (A)
Pdl P1 2.216(4) P1 Cl 1.85 (1)
Pdl P2 2.215 (4) P1 (:7 1.82 (1)
Pdl 01 2.195 (7) P1 C13 1.82 (1)
Pdl 010 2.177(8) P2 C19 1.83 (1)
Pdl 04 2.671 (7) P2 C25 1.82 (1)
Pdl 013 2.632 (7) P2 C31 1.80 (1)

 

Bond Angles

 

 

A B C A-B-C (°)
P1 Pdl P2 105.92 (8)
P1 Pdl 01 78.3 (2)
P1 Pdl 010 168.6 (2)
P2 Pdl 01 170.1 (2)
P2 Pdl 010 78.1 (2)
Pdl P1 CI 96.6 (4)
Pdl P1 C7 106.1 (4)
Pdl P1 C13 123.0 (4)
Pdl P2 C19 96.5 (4)
Pdl P2 C25 105.7 (4)

Pdl P2 C31 123.0 (4)

 

112

C43§19>02

 

C34 05C40

Figure 3.7. PLUTO drawing of Pd(TMPP—0)2 (17).

113

010) in a cis arrangement. Structure factors have not been well refined
due to a disorder in the crystal caused by interstitial CHzClz solvent
molecules.

(4) Reactions of [PdH(TMPP)2][BF4]2 (16) with Small
Molecules. Ligand insertions have been observed for the reactions of
Pd(II) and Pt(II) (P,O) complexes with small molecules such as 802, CO,
PhCN, and MeOzCCEC02Me.37 We have observed no reactions, however,
between 1 6 and 802, 2,2'-bpy, or MeOzCCECOzMe.

D. Reactions of PtII and TMPP.

(1) Syntheses. In attempts to prepare the Pt analogue of 16,
namely [Pt(TMPP)2][BF4]2, slow addition of an acetone solution containing
two equivalents of TMPP into an acetone solution containing
[Pt(NCCH3)4][BF4]2 was performed. The identical reaction was performed
in CH3CN due to the poor solubility of [Pt(NCCH3)4][BF4]2 in acetone, but
a shorter reaction time was required to avoid decomposition of TMPP in
CH3CN. [Pt(NCCH3)2(TMPP)2][BF4]2 (18) was obtained from these
reactions as verified by X-ray crystallography. Surprisingly, only two
(Il3CN ligands were substituted by monodentate TMPP molecules, which
suggest that the ether groups of the TMPP moiety are too weak to compete
with the nitrile ligands.

As it is known that transition metal complexes with ortho-
methoxyaryl phosphine ligands can undergo O-metallation (i. e.
demethylation) with co-coordinated halides (e. g. chloride and iodide) to
form metallacycles while MeX (X = halides) is released as a by-product,38
preparation of PtCTMPP-0)2 (1 9) was first achieved by the reaction of
PtC12(NCC6H5)2 with two equivalents of NaBPh4 and TMPP in THF,
which yielded a mixture of 19, PtCl(TMPP)(TMPP—0) (2 0), NaCl, and

114

[CH3-TMPP][BPh4]. Single crystals of Pt(TMPP—0)2 (1 9) were eventually
obtained from EtCN and Et20 solution of the products stored at 0 °C,
which suggests that the second O-metallation between the remaining ether
coordinated site and the remaining chloride ligand was slow and that more
forcing reaction conditions may be required; it is interesting to note this
was also observed in similar reactions reported by Shaw et al..38

Due to the slow demethylation of the second TMPP molecule, which

2TMPP [Pt(NCCH3)2(TMPP)2][BF4]2 (1 8)

/

{ Pt(TMPP- -0)2 (1 9)

[PthCH3)4llBF4]2

4 TMPP
2 [CH3-TMPP] [BF4]

, Pt(TMPP-0)2 (1 9)
1) 2 NaBPh4 +

2) 2 TMPP J PtCl(TMPP)(TMPP-0) (2 0)
+
/ ~ NaCl + [CH3-TMPP][BPh4]

PtC12(NCC6H5)2

 

PtCl(TMPP)(TMPP-0) (2 0)

+

2 TMPP {
MeCl + [CH3-TMPP]C1

Scheme 3.2 Reactions of Pt(II) starting materials with TMPP.

is on the same time scale as the decomposition of the TMPP moiety,

Pt(TMPP-0)2 was obtained in better yields from slow addition of an

acetone solution containing four equivalents of TMPP into an acetone
solution containing [Pt(NCCH3)4][BF4]2. PtCl(TMPP)(TMPP-0) (2 0) was

115

then deliberately prepared from the reaction of PtC12(NCC6H5)2 with two
equivalents of TMPP in THF as described in Scheme 3.2.

(2) NMR Studies of 18, 19 and 20. The room temperature 1H
NMR spectrum of [Pt(NCCH3)2(TMPP)2][BF4]2 (18) (Figure 3.8) reveals
six distinct resonances in the methoxy region between 3.3 and 3.9 ppm and
two distinct resonances in the meta proton region between 6.1 and 6.2 ppm
due to the TMPP ligands. This complicated pattern shown in Figure 3.8
does not agree with the solid state structure of [Pt(NCCH3)2(TMPP)2]-
[BF4]2 (18) with TMPP moieties in an n1 mode (see below) and further
indicates that the solution structure of 18 possesses two types of TMPP
rings. This observation is surprising given the fact that the solution
structures of these TMPP compounds tend to be less rigid than the
corresponding solid state structure. A proposed solution structure of
[Pt(NCCH3)2(TMPP)2][BF4]2 as well as the assignment of the resonances is
indicated below. Two rings, above and below the axis defined by P-Pt-P,
of the TMPP ligand are symmetry related by the mirror plane defined by

OMe(e)
H(Z) O H(Z)
(d)MeO : OMe(d)
R NCMe(a) OMe(b) H ( 1 )

 

 

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the third ring, the two phosphorus atoms and the metal center, which
results in two types of resonances assigned to the TMPP ligands by NMR
spectroscopy. One singlet at 3.33 ppm is assigned to two CH3CN (a), while
the resonances at 3.41 and 3.78 ppm are assigned to be the ortho (b) and
para (c) methyl groups on the rings of the TMPP ligands far away from
CH3CN. The two resonances at 3.61 and 3.82 ppm are assigned to the
ortho (d) and para (e) methyl groups on the rings of TMPP ligands in close
proximity to CH3CN. The triplet and the doublet are due to four
equivalent meta (1) protons on the rings distal from the CH3CN ligand and
eight protons (2) on the rings in close proximity to CH3CN. The triplet
observed in the meta proton region of the TMPP ligand indicates a trans

geometry of two phosphorus atoms, which is accord with the solid state
structure of [Pt(NCCH3)2(TMPP)2][BF4]2.

The room temperature 1H NMR spectrum of Pt(TMPP-0)2 (19)
(Figure 3.9) resembles that of Pd(TMPP-0)2 and reveals four distinct
resonances in the methoxy region of TMPP ligand between 3.3 and 3.9
ppm. This indicates that the unbound rings of the TMPP ligand are free to
rotate which has also been observed in the Ni(Il) 220 and Pd (II) analogues
as described in Section C. Two of these four resonances are due to the
inequivalent ortho and para methyl groups of the bonded ring and the other
two are due to four equivalent ortho and two equivalent para methyl
groups of the free rings. Three distinct resonances in the meta proton
region of TMPP ligand between 5.5 and 6.2 ppm. Two of this three
resonances are due to two inequivalent meta protons of the bonded ring and
the last one is due to four equivalent meta protons of the free rings. A 31P
NMR spectrum of Pt(TMPP-0)2 in acetonitrile-d3 at room temperature

exhibits a single resonance at 6 = -24.97 ppm with the platinum-phosphorus

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Figure 3.12. Proposed structure for PtClCTMPP)(TMPP-0) (2 0).

122

couping constant 1th-p of 1950 Hz, which is in the range of values
reported in the literature.39 These NMR data are in accord with the
presence of two types of unsymmetrically coordinated rings of the tertiary
phosphine ligand.
The room temperature 1H NMR spectrum of PtCl(TMPP)(TMPP-0)
(2 0) (Figure 3.10) reveals five distinct resonances in the methoxy region
of the TMPP and TMPP-0 ligands between 3.2 and 3.9 ppm. Once again
this is an indication of the monodentate TMPP ligand participating in a
dynamic process and free rotation of the unbound rings of the bidentate
TMPP ligand. Two of these five resonances are due to the inequivalent
ortho (a) and para (b) methoxy groups of the bonded ring of the TMPP-0
moiety, while a second set are due to the para (c and d) methoxy groups on
the free rings of the TMPP and TMPP-0 ligands. The last of these five
resonances is due to ten accidentally equivalent ortho (e) methoxy groups
on the free rings of the TMPP and TMPP-0 ligands. Four distinct
resonances in the meta proton region of TMPP and TMPP-0 ligands
between 5.3 and 6.1 ppm. Two multiplets at 5.29 and 5.38 ppm are due to
the meta (1 and 2) protons of the bonded ring of the TMPP-0 moiety,
while a doublet at 6.04 ppm is due to the meta (3) protons of the free rings.
The last doublet at 5.99 ppm is due to six equivalent meta (4) protons of
the nl-TMPP ligand. A 31P NMR spectrum of 20 in acetonitrile-d3 at
room temperature exhibits a complicated pattern as shown in Figure 3.11.
This is a typical pattern for two inequivalent phosphorus atoms coupled to
a platinum nucleus (195Pt, I = 1/2, 33% abundance).33:39 Preliminary
simulation failed to provide the chemical shifts as well as the definitive
coupling constants, 2] (PP) and 1J(PtP). However, the pattern did reveal a
large magnitude for the coupling constant 2.1(PA-PB), which is due to the

123

trans geometry of two phosphines. According to these NMR data, the
structure is proposed to be as depicted in Figure 3.12.

(3) Molecular Structures of 18 and 19. ORTEP drawings of
the compounds [Pt(NCCH3)2(TMPP)2][BF4]2 (18) and Pt(TMPP-0)2 (19)
are presented in Figures 3.13 and 3.15, while selected bond distances and
angles are presented at Tables 3.6 and 3.7, respectively. The molecular
geometry of 1 8 consists of a square planar arrangement of two trans
phosphorus atoms and two CH3CN ligands, with the TMPP ligand bound to
the Pt atom in an n1 mode. The molecular geometry of 19 consists of a
distorted square planar arrangement with a cis arrangement of phosphorus
and methoxy-oxygen atoms about the metal center and long axial
interactions with two ether-oxygen atoms from the TMPP moieties. The
Pl-Ptl-Nl and P2-Ptl-N2 angles are 87.0 (2)° and 90.3 (2)°, respectively,
leading to a nearly perfect square planar geometry around the metal center.
No steric repulsion was observed for the trans ligands (T MPP and
(113CN), as supported by the angles of P1-Pt1-P2 and N1-Pt1-N2 of
175.67 (7)° and 177.0 (3)°, respectively. The distortion observed in
Pt(TMPP-0)2 is due to ring strain, evident by the angles Ptl-Pl-Cl-C2-Ol
of 84.1 (2)° and Ptl-P2-C19—C20-010 of 84.2 (2)° compared to the free
Ill-TMPP ligands observed in compound [Pt(NCCH3)2(TMPP)2][BF4]2
(18). Free rotation of arene rings on 111-TMPP ligands of 1 8 is effectively
blocked due to the presence of CH3CN ligands, which are in the rotational
pathway of pedant methoxy groups of TMPP moeties as depicted in a space
filling diagram of the compound (Figure 3.14). This again supports the

solution behavior of this compound by NMR spectroscopies as mentioned

earlier.

124

Table 3.5. Summary of crystallographic data for [Pt(NCCH3)2-
(TMPP)2][BF4]2 (18) and Pt(TMPP-O)2-3EtCN (1 9-3EtCN).

 

 

Compound 18 l9-3EtCN
formula PtP2018N2C53H7232F3 PtP2013C61H75N3
formula wt 1515.85 1395.31
space group P-l P21/c

a, A 14.578 (3) 12.958 (5)

b, A 18.291 (3) 33.262 (7)

c, A 13.229 (2) 14.697 (5)

0t, deg 104.40 (1) 90

[3, deg 109.24 (1) 100.68 (3)

7, deg 88.41 (2) 90

v, A3 3220 (1) 6225 (3)

Z 2 4

dclac, g/cm3 1.563 1.489

11, cm-l 23.38 23.96
temp,°C -100i1 -100i1

Ra 0.036 0.042

wa 0.045 0.047

 

3R = XllFol - IFcII/ZlFol- b Rw = [ZwlFol - ch02/ZWIFolzll’2; w = 08201201).

125

 

 

 

 

014
C11 Q
09 C71 I (:23
on k C40 c
G? r . .8“ .. w ‘9“
06 c \
04120" ~ 616 P, x 012 J 026°“ 010°“
c1: 03 J . 92
1
0‘ m 013 ‘ o" 054
037 C2 07 N2 0“ 31 03‘
cs
cs1 .. ca:
ca 043 es: 035
04
(:32 C33 C34
02
ms 017
(:53

Figure 3.13. ORTEP drawing of. [Pt(NCCH3)2(TMPP)2][BF4]2 (18).

126

 

Figure 3.14. Space filling diagram of [Pt(NCCH3)2(TMPP)2][BF4]2 (18).

127

Table 3.6. Selected bond distances (A) and bond angles (°) for

[Pt(NCCH3)2(TMPP)2][BF4]2 (1 8).
Bond Distances

 

 

 

 

 

A B A-B (A) A B A-B (A)

Ptl P1 2.357 (2) P1 C1 1.822 (7)

Pt] P2 2.356 (2) P1 C7 1.814 (7)

Pt] N1 1.972 (7) P1 C13 1.806(7)

Ptl N2 1.961 (6) P2 C19 1.810(7)

N1 C71 1.12 (1) P2 C25 1.808 (7)

N2 C81 1.141 (9) P2 C31 1.820(7)
Bond Angles

A B C A-B-C (°)

P1 Ptl P2 175.67 (7)

P1 P11 N1 87.0(2)

P1 Ptl N2 93.9 (2)

P2 Ptl N1 88.9 (2)

P2 Ptl N2 90.3 (2)

N1 Ptl N2 176.9(3)

Ptl N1 C71 171.9 (8)

Pt] N2 C81 174.0 (6)

N1 C71 C72 176(1)

32 C81 C82 178.7 (8)

 

128

  
  
 

.-/ C48
$1028 08

\
C27 \9/ \‘A C29

    
 

,iv/

. , ,‘ ‘ ' ‘1‘! 02

Figure 3.15. ORTEP drawing of Pt(TMPP—0)2 (l9).

129

Table 3.7. Selected bond distances (A) and bond angles (°) for

Pt(TMPP-0)2-3EtCN (l 9-3EtCN).
Bond Distances

 

 

A B A-B (A) A B A-B (A)
P11 P1 2.255 (2) P1 C1 1.810(8)
Ptl P2 2.255(2) P1 C7 1.821 (9)
Ptl 01 2.044 (5) P1 C13 1.830 (8)
Ptl 010 2.049 (5) P2 C19 1.817 (8)
P11 09 3.110 (5) P2 C25 1.836 (9)
Ptl 018 3.130 (7) P2 C31 1.845 (9)

 

Bond Angles

 

 

A B C A-B-C (°)
P1 Ptl P2 110.85 (8)
P1 Ptl 01 84.1 (2)
P1 Ptl 010 164.0 (2)
P2 Ptl 01 163.2 (2)
P2 Ptl 010 84.2 (2)
Ptl P1 CI 98.7 (3)
Ptl P1 C7 111.9 (3)
Ptl P1 C13 123.5 (3)
Ptl P2 C19 99.1 (3)
Ptl P2 C25 111.0 (3)

it] P2 C31 124.0 (3)

 

130

The average Pt-P bond distances of [Pt(NCCH3)2(TMPP)2][BF4]2
and Pt(TMPP-0)2 (2.356(2) and 2.255 (2) A respectively) are similar to
those that been observed (2.2 to 2.4 A) in phosphine and phosphite
complexes of Pt(II).39 The nl-Pt-P bond distances in
[Pt(NCCH3)2(TMPP)2][BF4]2 are longer than those found in Pt(TMPP—
0)2, which can be attributed, in part, to the chelate effect of the nZ-TMPP
ligands. The average Pt-O bond distance of 2.047 (5) A in Pt(TMPP-0)2
is longer than the corresponding bond distance reported in the platinum-
alkoxide complex, cis-[Pt(PPh2CI-IzCMe7_0)2] (2.013 (4) A) 40a and cis-
[Pt(thPCH2CI-120)2]-H20 (2.039 (5) A) 40b, but shorter than that found in
two platinum-ether complexes (2.144 (9) A and 2.192 (7) A) 40041. Axial
interactions in the molecule Pt(TMPP—0)2 that involve the Pt center and
pendant methoxy groups are longer than the sum of the covalent radii of
the two atoms (Ptl-O9 = 3.110(5) A and P11-018 = 3.130(7) A).

E. Reactions of Cd11 and TMPP.

(l) Syntheses. Cd(N03)2(TMPP) (21) was obtained from the
reaction of Cd(N03)2-4(HzO) with TMPP. Altering the stoichiometry of
the Cd(II) and TMPP reactants does not affect the course of the reaction, as
compound 2 1 was obtained as the only product from both reactions with
Cd(II) and TMPP in a ratio of either 1:] or 1:2. It appears that the nitrate
ligands are not as labile as expected, therefore the Cd(II) atom can
accommodate only one incoming TMPP ligand along with two coordinated
nitrate groups. The combination of these ligands bound to the metal center
results in a distorted octahedral geometry for the compound.

Attempts to prepare a homoleptic (TMPP-0) complex of Cd(II)
from (CdC12-2.5(H20)) and TMPP produced CdC12(TMPP)2 (2 2) with no
demethylation being observed. In order to prepare [Cd(TMPP)2]2”, the

131

nitrate abstraction reagent such as NaBF4 41 was introduced in situ to the
reaction solution of Cd(N03)2-4(I-120) and TMPP which produced
[Cd(TMPP)2][BF4]2 (2 3) with NaNO3 as the by—product.

(2) NMR Studies of 21-23.

A room temperature 1H NMR spectrum of Cd(N03)2(TMPP) (21)
(Figure 3.16) revealed three distinct resonances in the range of 3.4—3.9
ppm and two distinct resonances in the range of 6.1-6.3 ppm due to the
TMPP ligand. This pattern indicates that there are two slightly different
111-TMPP moieties with their para methoxy groups accidentally being
equivalent as depicted in Figure 3.16. Although there are two
enantiomorphs found in the solid state structures of 2 1, one would expect
that both enantiomorphs would behave similarly in solution.
Crystallization of Cd(N03)2(TMPP) from more polar solvents such as
CHzClz, however, produced the same crystalline form of
Cd(N03)2(TMPP) as determined by the cell parameters obtained from X-
ray crystallography. This result indicates that the nitrates are tightly
bonded to the metal center rather than being non-coordinating counterions,
a situation that allows only one TMPP molecule to bind to the metal center.
Therefore, the solution behavior of Cd(N03)2(TMPP) may involve some
complicated arrangement, which leads to two slightly inequivalent TMPP
moieties in an n1 mode.

The room temperature 1H NMR spectrum of CdC12(TMPP)2 (2 2)
revealed two distinct resonances at 3.59 and 3.76 ppm and one doublet at
6.07 ppm due to the TMPP ligands. The two singlets in the methoxy
region are due to twelve equivalent ortho methoxy groups and six
equivalent para methoxy groups. The doublet in the meta proton region is

due to twelve equivalent meta protons. This indicates an n1 bonding mode

132

 

 

 

8-8888 8 :3 882528280 mo 888% E22 E .28 9:8:

 

 

 

 

133

of TMPP as described in Chapter 2. In addition to this, two stretching
vibrations of v(Cd-Cl) were observed at 258 and 242 cm"1 by IR
spectroscopy, which supports its assignment as a monomeric complex of
sz skeletal symmetry.42

The room temperature 1H NMR spectrum of [Cd(TMPP)2][BF4]2
consists of two distinct resonances at 3.48 and 3.86 ppm and one triplet at
6.23 ppm attributable to the TMPP ligands. The two singlets in the
methoxy region are assigned to twelve equivalent ortho methoxy groups
and six equivalent para methoxy groups, whereas the triplet in the meta
proton region is due to twelve equivalent meta protons. These data clearly
indicate that only one type of arene ring is present and that the TMPP
moieties are bound to the Cd(II) center in an n1 mode. In addition to that,
the virtual triplet observed in the meta proton region further indicates a
trans geometry of the two phosphines, in accord with its solid state
structure as described below.

(3) Molecular Structures of 21 and 23. An ORTEP drawing
and selected bond distances and angles of compound Cd(N03)2(TMPP)
(2 1) are presented in Figure 3.17 and Table 3.9. The molecule exhibits a
distorted octahedral geometry with the Cd atom residing in the center of a
distorted octahedron which resembles a trigonal prism defined by one
phosphorus atom (from the TMPP ligand) and five oxygen atoms. Four of
these five oxygen atoms are from two bidentate nitrates which bind to the
metal center through oxygen atoms, and the last one is from the ether-
methoxy group of an 112-TMPP ligand. The Cd-P distance of 2.435 (5) A is
shorter than that of 2.459 (1) A for the terminal P(SiMe3)2 in
{Cd[P(SiMe3)2]2}2 43a and longer than that of 2.427 (1) A m
Cd[P(SiPh3)2]2 449. The Cd-O distances for the nitrates range from 2.30

134

Table 3.8. Summary of crystallographic data for Cd(TMPP)(N03)2 (21)
and [Cd(TMPP)2][BF4]2 (2 3).

 

 

Compound 21 23
formula CdPO15C27l-I33N2 CdP2013C54H66B2F3
formula wt 768.95 1351.06
space group Pn821 C2/c

a, A 15.060 (4) 39.92 (1)
b, A 11.918 (4) 11.164 (7)
c, A 18.470 (6) 32.336 (8)
01, deg 90 90

0, deg 90 121.46 (1)
Y, deg 90 90

v, A3 3315 (3) 12293 (8)
Z 4 8

dclac, g/cm3 1.540

11, cm-l 7.7

temp,°C -100i1 -100i1
Ra 0.049

wa 0.063

 

a R = XllFol - chII/ZlFol- b Rw = [ZWIFoI - |FCDZIZW|FO|2]1/2; W = 1/02(|Fo|)-

135

 

 

 

Figure 3.17. ORTEP drawing of Cd(N03)2(TMPP) (21).

136

Table 3.9. Selected bond distances (A) and bond angles (°) for

Cd(TMPP)(N03)2 (2 1).

Bond Distances

 

 

 

 

 

A B A-B (A) A B A-B (A)
Cdl P1 2.435 (5) 011 N1 1.23 (2)
Cdl 06 2.56 (1) 012 N1 1.29 (3)
Cdl 011 2.30 (1) 013 N1 1.21 (2)
Cdl 012 2.53 (2) 021 N2 128(2)
Cdl 021 2.30 (1) 022 N2 1.20 (2)
Cdl 022 2.34 (1 ) 023 N2 1.23 (2)
Bond Angles
A B C A-B-C A B C A-B-C
(°) (°)
P1 C111 06 72.5 (3) 011 N1 012 118 (2)
P1 Cdl 011 131.7 (4) 011 N1 013 125 (2)
P1 C111 012 103.2 (5) 012 N1 013 118 (2)
P1 Cdl 021 128.3 (4) 021 N2 022 115 (1)
P1 Cdl 022 134.6 (4) 021 N2 023 120 (2)
011 Cdl 012 52.8 (5) 022 N2 023 125 (2)
021 Cdl 022 53.9 (5)

 

137

cs0
0,4 4’
027
’ ”C28
5 5029 C54
. 9 °
025
5:9 acsa
’2 ale” 4’

 

 

C45- ”5’ P1 Ct“ 016 5', C340” CS1
’ ”a, , C33 012
039 ’01 99‘5“” C19 ’
cs9 0 a, 010 Q

1
’ ’ C46 , ~(324 C48
cs 2 02
’ ’ ”C23

04 a 5 03 C37 c2150”
1
a a 02 1, 01
C38 5 C47

Figure 3.18. PLUTO drawing of [Cd(TMPP)2][BF4]2 (23).

138

(l) to 2.53 (2) A, which are typical (2.38-2.56 A) of the distances found
for mono- and bi-dentate nitrates.41144 The distance of Cd1-012 (2.53 (2)
A), however, is 0.2 A longer than the other three corresponding distances
(Cdl-Oll (2.30 (1) A), Cd1-021 (2.30 (1) A), and Cd1-022 (2.34 (1) A)),
which may be due to steric repulsion caused by the bulky TMPP ligand.
The distance between the ether-oxygen atom in TMPP and the Cd(II) atom
is 2.56 (1) A, which is much longer than the corresponding distance
reported for [Pd(TMPP)2][BF4]2 (2.186(8) A). This indicates a very weak
interaction between the ether group and the metal center, which is not
surprising given the solution structure of Cd(N03)2(TMPP) as determined
by 1H NMR spectroscopy (i. e. monodentate TMPP was observed in
solution but the TMPP is bidentate in the solid state).

X-ray quality single crystals of [Cd(TMPP)2][BF4]2 (2 3) were
grown by slow diffusion of diethyl ether into a CH2C12 solution of the
compound. A PLUTO drawing of [Cd(TMPP)2][BF4]2 is presented in
Figure 3.18. The Cd(II) atom resides in the center of a distorted tetragonal
environment defined by two phosphorus atoms (P1, P2) and two methoxy-
oxygen atom (04, 07), where the TMPP ligands are bound to the metal
center in an n1 and an n3 mode. The two P atoms are in an approximate
trans arrangement, which is accord with the observation of the virtual
triplet in the 1H NMR spectrum of 23. Structural factors have not yet been
well refined due to the disorder of [BF4]" ions in the crystal of
[Cd(TMPP)2][BF4]2. Complexes of Cd(II) are known as four, five, or six
coordinate,45 while there is only one example of a two coordinate complex
reported to date in our knowledge.43b If refinement goes well, the
molecule [Cd(TMPP)2][BF4]2 may exhibit either a six- or two-coordinate

139

geometry with TMPP ligands depending upon whether they are n3 or 111,
respectively.
4. Summary

The chemistry of group VIII divalent and trivalent metals with
TMPP has produced some unusual compounds such as the first Ni(II)/(III)
pair supported by an ether-phosphine ligand and the first example of
octahedral Pd(II) complexes possessing the shortest axial contacts. Unlike
most (P,O) ligands,1 the TMPP moiety is flexible enough to adopt a myriad
of bonding modes as demonstrated here, from monodentate (1 8), bidentate
(l 7, 1 9), to tridentate (1 5 and 1 6). The expected reactive ether-phosphine
complex [Pd(TMPP)2][BF4]2 (l 6), however, failed to produce any
promising reactions with key small molecules. The difficulty in preparing
homoleptic (T MPP-O) complexes of group VIII is due to the "non-
innocent" character of the TMPP molecule, which participates in side
reactions with nucleophiles to give phenoxide products. It is worth noting
that the TMPP molecule itself is the best candidate as a demethylation
reagent for syntheses of the pure M(TMPP-0)2 complexes (M = Ni, Pd,
and Pt) as other nucleophiles are less specific and lead to lower yields of
the desired product.

Finally, the chemistry of Cd(II) with phosphine ligands is scarce.
The reactions of Cd(II) with TMPP described in this work produce nitrate-
containing or nitrate-free products depending on the absence or presence of

a nitrate abstraction reagent.

10.

140

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DIFABS: Walker, N., Stuart, D. Acta Cryst. 1983, A39, 158.

PHASE: Calbrese, J. C.; PHASE - Patterson Heavy Atom Solution
Extractor. University of Wisconsin-Madison, Ph. D. Thesis (1972).

(a) Dunbar, K. R.; Quillevéré, A.; Dunham, W. R. Polyhedron
1993, 12, 807. (b) Dunbar, K. R.; Quillevéré, A Angew. Chem.
Int. Ed. Engl. 1993, 32, 293.

33.
34.

35.

36.
37.

38.

39.

40.

41.

42.

43.

143

A. Quillevéré, Michigan State University, Ph. D. Thesis (1992).

(a) Haines, J.; McAuley, A. Coord. Chem. Rev. 1981, 39, 94. (b)
Lappin, A. G.; McAuley, A. Adv. Inorg. Chem. 1988, 32, 241.

Zimmer, M.; Schulte, G.; Luo, X. -L.; Crabtree, R. H. Angew.
Chem. Int. Ed. Engl. 1991, 30, 193.

S. C. Haefner, Michigan State University, Ph. D. Thesis (1992).

Alcock, N. W.; Platt, A. W. 6.; Powell, H. H.; Pringle, P. G. J.
Organomet. Chem. 1989, 361 , 409 and references therein.

(a) Miller, E. M. and Shaw, B. L. J. Chem. Soc., Dalton Trans.
1974, 480. (b) Jones, C. E.; Shaw, B. L.; Turtle, B. L. J. Chem.
Soc., Dalton Trans. 197 4, 992. (c) Empsall, H. D.; Shaw, B. L.;
Turtle, B. L. J. Chem. Soc., Dalton Trans. 1976, 1500. (d)
Empsall, H. D.; Heys, P. N.; Shaw, B. L. J. Chem. Soc., Dalton
Trans. 1978, 257.

(a) Comprehensive Coordination Chemistry; Wilkinson, G.; Gillard,
R. D.; McCleverty, J. A., Eds.; Pergamon Press: Oxford, England,
1987; vol 5; chap. 52 and references therein.

(a) Alcock, N. W.; Platt, A. W.; Pringle, P. J. Chem. Soc., Dalton
Trans. 1987, 2273. (b) Alcock, N. W.; Platt, A. W. G.; Pringle, P.
G. J. Chem. Soc., Dalton Trans. 1989, 139. (c) Anderson, G. K.;
Corey, E. R.; Kumar, R. Inorg. Chem. 1987, 26, 97. (d) Alcock,
N. W.; Platt, A. W. G.; Pringle, P. G. J. Chem. Soc., Dalton Trans.
1987, 2069.

Looney, A.; Saleh, A.; Zhang, Y.; Parkin, G. Inorg. Chem. 1994,
33, 1158.

(a) Goel, R. G.; Henry, W. P.; Srivastava, R. C. Inorg. Chem. 1981,
20, 1727. (b) Goel, R. G.; Henry, W. P.; Jha, N. K. Inorg. Chem.
1982, 21, 2551 and references therein.

(a) Goel, S. C.; Chiang, M. Y.; Buhro, W. E. J. Am Chem. Soc.
1993, 115, 160. (b) Matchett, M. A.; Chiang, M. Y.; Buhro, W. E.
Inorg. Chem. 1994, 33, 1109.

(8) Cameron, A. F.; Taylor, D. W.; Nuttall, R. H. J. Chem. Soc.,
Dalton Trans. 1972, 1608. (b) Griffith, E. A. H.; Charles, N. G.;
Rodesiler, P. F.; Amma, E. L. Polyhedom 1985, 4, 615. (c)

45.

144

Banerjee, A.; Brown, C. J .; Jain, P. C.; Gautam, P. Acta Crystallogr.
1983, C39, 331. (d) Griffith, E. A. H.; Charles, N. G.; Rodesiler,
P. F.; Amma, E. L. Acta Crystallogr. 1984, C40, 1161. (e)
Rodesiler, P. E; Turner, R. W.; Charles, N. G.; Griffith, E. A. H.;
Amma, E. L. Inorg. Chem. 1984, 23, 999. (f) Kleywegt, G. J.;
Wiesmeijer, W. G. R.; Van Driel, G. J .; Driessen, W. L.; Reedijk, J.;
Noordik, J. H.; J. Chem. Soc., Dalton Trans. 1985, 2177.

(a) See for example: (a) F. A. Cotton, G. Wilkinson, Advanced
Inorganic Chemistry, 5th Ed.; John Wily and Sons, Inc.; New York,
1988. (b) Castineiras, A.; Arguero, A.; Masaguer, J. R.; Ruiz-Amil,
A.; Martinez-Carrera, 8.; Garcia-Blanco, S. Polyhedron, 1985, 4,
143. (c) Cases, J. 8.; Sanchez, A.; Bravo, J. Garcia-Fontan, 8.;
Castellano, E. E.; Jones, M. M. Inorg. Chim. Acta 1989, 158, 119.

CHAPTER IV

CHEMISTRY OF METAL HALIDE COMPLEXES WITH A
PHOSPHONIUM HALIDE AND OTHER ORGANIC HALIDES

145

146

1. Introduction

High spin ferrous and ferric compounds are of obvious interest in
magnetic studies, from both the biological1 and materials perspectives?
Compared to ferric systems, the magnetic behavior of dinuclear and
polynuclear ferrous systems have not been investigated as thoroughly, due,
in part, to the large zero-field splittings and substantial anisotropies of the
magnetic hyperfine interactions.

Earlier in our laboratories, it was discovered that reactions of ferric
chloride FeCl3 with TMPP produced an unexpected molecule [H-
TMPP]2[Fe2C16], wherein two Fe(II) centers are ferromagnetically
coupled.3a This interesting discovery led to the investigation of a series of
dinuclear complexes containing the [Fe2Cl6]2‘ unit with a variety of
counterions. This work makes an interesting comparison to the well-
documented series of hydroxo-bridged Cu(II) dinuclear complexes with
different bridging angles (Cu-O-Cu) that affect their magnetic properties.4
The magnetic properties of the new diferrous dinuclear complexes were
also studied to attempt a correlation of the bridging angles (Fe-Cl-Fe) with
the magnetic behavior of these type of compounds. In addition, a
tetranuclear cluster Fe4C13(THF)6 was accidentally produced in our
laboratories during these studies, which had been previously characterized
but for which no complete magnetic studies had been reported.5

Both the dinuclear and tetranuclear compounds are being explored
for their potential to serve as pure, soluble precursors to large clusters and
low-dimensional magnetic materials. The 2,2'-bipyrimidine (2,2'-bpym)
molecule is able to act as an bidentate ligand to connect two paramagnetic
centers together to form a polymeric structure. In fact, polynuclear

complexes containing the 2,2'-bipyrimidine ligand have been much studied,

147

in order to establish the correlation between structure and magnetic
properties.6 The 2,2'-bpym molecule has primarily been applied to a series
of inorganic compounds with magnetically active transition metals such as
Cu7fiab and C070. This chapter describes the syntheses and magnetic studies
of dinuclear and polynuclear Mn(II), Co(II) and Fe(II) complexes and their
reactions with 2,2'-bpym as well as other nitrogen donors along with the
synthesis of a new Mn(II) complex with 2,2'-bipyrimidine ligands.
2. Experimental Section
A. Physical Measurements

Infrared spectra were recorded on a Nicolet 740 FT -IR
spectrophotometer. Elemental analyses were performed at Desert Analysis,
Tucson, AZ. SQUID measurements were performed on Quantum Design
susceptometers housed in the Physics and Astronomy Department at
Michigan State University and supported by the Center For Fundamental
Materials Research at Michigan State University.
B. Synthesis

The starting materials FeC12 and CoClz were purchased from Strem
Chemicals, Inc., while MnC12 was purchased from Aldrich and used
without further purification. Tris(2,4,6-trimethoxyphenyl)phosphine
(TMPP) was prepared according to published methods or purchased from
Aldrich and used without further purification.8 [H-TMPP]CI was prepared
by the reaction of TMPP with HCl.9 PPh4Cl (tetraphenylphosphonium
chloride) and AsPh4Cl (tetraphenylarsonium chloride) were purchased from
Lancaster Synthesis, while Et4NCl (tetraethylammonium chloride) was
purchased from Sigma Chemical Co.; all used as recieved. Me3NHCl
(trimethylammonium chloride), BzNEt3Cl (benzyltriethylammonium

chlororide), ppnCl (bis(triphenylphosphonium)imminium chloride) were

148

purchased from Aldrich, while NH4C1 (ammonium chloride) was purchased
from EM Science. Acetone was distilled over 3 A molecular sieves.
Benzene, diethyl ether, THF, and toluene were distilled over sodium-
potassium/benzophenone, whereas methylene chloride was distilled over
P205 under a nitrogen atmosphere. Unless otherwise specified, all
reactions were carried out under an argon atmosphere by using standard
Schlenk-line techniques.

(1) Preparation of [H-TMPP]2[Fe2Cl¢] (24).

An acetone solution (15 mL) of [H-TMPP]CI (0.370 g, 0.650 mmol)
was added to an acetone solution (15 mL) of FeC12 (0.082 g, 0.650 mmol),
and the resulting reaction solution was stirred for 12 h to give a pale yellow
precipitate and a yellow solution. The yellow solution was filtered through
Celite along with acetone washings (20 mL) of the precipitate. After
concentration of the filtrate, followed by slow precipitation with Et20, an
off-white compound was obtained (yield: 0.365 g, 81% based on FeC12).
IR (Nujol, cm'l): 1594 (s), 1577 (s), 1410 (m), 1338 (m), 1305 (w), 1230
(ms), 1206 (ms), 1180 (w), 1157 (m), 1133 (ms), 1100 (m, br), 1023 (m),
948 (w), 927 (w), 913 (w), 884 (w) 819 (w), 643 (w); v(FeCl) 360 (m), 310
(m), 288 (m), 234 (m). ueff = 8.15 1.113 at 300K (0.1T).

(2) Preparation of [PPh4]2[Fe2C16] (25).

The compound [PPh4]2[Fe2Cl6] was prepared in an identical manner
as described in (1) from the reaction of PPh4Cl (0.887 g, 2.367 mmol) and
FeC12 (0.300 g, 2.367 mmol) in 0.854 g (yield: 72% based on FeC12). IR
(Nujol, cm'l): 1585 (w), 1483 (w), 1436 (ms), 1338 (w), 1313 (w), 1161
(w), 1109 (s, br), 1071 (m), 1028 (m), 995 (m), 758 (ms), 749 (m, sh), 720
(s), 687 (s), 616 (w), 525 (8, br), 447 (w); v(FeCl) 340 (ms), 290 (m), 238

149

(111). [Jeff = 7.19 1113 at 300K (0.1T). Anal. Calcd for Fe2C16P2C43H40: C,
57.46; H, 4.02; CI, 21.20. Found: C, 57.08; H, 3.88; CI, 21.03.
(3) Preparation of [Et4N]2[Fe2C16] (26).

The compound [Et4N]2[Fe2Cl6] was prepared in an identical manner
as described in (1) from the reaction of Et4NCl (0.327 g, 1.972 mmol) and
FeC12 (0.250 g, 1.972 mmol) in 0.426 g (yield: 74% based on FeC12). IR
(Nujol, cm'l): 1404 (m), 1305 (mw), 1184 (s), 1081 (m), 1033 (s, br), 1006
(ms, br), 801 (s, br), 467 (w); v(FeCl) 379 (m), 344 (s), 298 (s), 240 (s).
“eff: 7.25 113 at 300K (0.1T).

(4) Preparation of [ppn]2[Fe2Cl6] (27).

The compound [ppn]2[Fe2C16] was prepared in an identical manner
as described in (1) from the reaction of ppnCl (0.453 g, 0.789 mmol) and
FeC12 (0.100 g, 0.789 mmol) in 0.415 g (yield: 75% based on FeC12). IR
(Nujol, cm‘l): 1586 (w), 1480 (mw), 1438 (m), 1265 (ms, br), 1178 (w),
1166 (w), 1114 (s, br), 1026 (w), 997 (m), 801 (w), 796 (w, sh), 757 (mw,
sh), 747 (m), 720 (s), 691 (s), 549 (s), 530 (s), 499 (s); v(FeCl) 395 (m),
346 (s), 294 (s), 237 (s). Hoff = 5.12 1113 at 300K (0.1T). Anal. Calcd for
Fe2C16N2P4C72H6o: C, 61.70; H, 4.31; CI, 15.18. Found: C, 61.85; H,
4.32; CI, 15.02.

(5) Preparation of [AsPh4]2[Fe2Cl6] (28).

The compound [AsPh4]2[Fe2C15] was prepared in an identical
manner as described in (1) from the reaction of AsPh4Cl (0.185 g, 0.442
mmol) and FeC12 (0.056 g, 0.442 mmol) in 0.185 g (yield: 77% based on
FeC12). IR (Nujol, cm‘l): 1570 (w), 1483 (mw), 1438 (m), 1336 (mw),
1310 (mw), 1185 (w), 1162 (w), 1082 (ms), 1022 (w), 996 (m), 750 (s), 738
(s), 686 (s), 614 (w), 476(8), 459 (s); v(FeCl) 340 (8, br), 289 (m), 239 (In).

150

ueff = 7.23 1.113 at 300K (0.1T). Anal. Calcd for Fe2Cl6AszC43H40: C,
52.84; H, 3.40; CI, 19.50. Found: C, 53.86; H, 3.68; CI, 20.21.
(6) Preparation of [BzNEt3]2[Fe2Cl6] (29).

The compound [BzNEt3]2[Fe2Cl6] was prepared in an identical
manner as described in (1) from the reaction of BzNEt3Cl (0.300 g, 1.317
mmol) and FeC12 (0.167 g, 1.317 mmol) in 0.300 g (yield: 64% based on
FeC12). IR (Nujol, cm-l): 1711 (w), 1601 (w), 1303 (m), 1210 (w), 1152
(m), 1078 (ms), 1054 (ms, br), 1029 (ms, br), 788 (w), 747 (m), 700 (m),
537 (w), 492 (w), 460 (w); v(FeCl) 350 (s, br), 281 (s, br), 239 (s br). ueff
= 6.6 113 at 300K (0.1T). Anal. Calcd for Fe2Cl6N2C26H44: C, 44.04; H,
6.25; CI, 30.00. Found: C, 44.44; H, 6.33; CI, 29.98.

(7) Reaction of FeC12 and Me3NHCl.

An acetone solution (15 mL) of Me3NHCl (0.151 g, 1.578 mmol)
was added to an acetone solution (15 mL) of FeC12 (0.200 g, 1.578 mmol),
and the reaction solution was stirred for 12 h. The resulting solution was
filtered through Celite to give a yellow filtrate and the solvent was removed
by evaporation under vacuum to give a pale yellow solid. The solid was
redissolved in MeOH, then filtered through Celite to yield a pale yellow
filtrate. After concentration of the pale yellow filtrate, followed by slow
precipitation with Et20, an off-white compound was obtained (yield: 0.291
g). IR (Nujol, cm'l): 1487 (s), 1406 (m), 1416 (m), 1259 (w), 1226 (w),
1050 (s), 974 (s), 815 (m), 467 (w); v(FeCl) 381 (w), 289 (w), 263 (m, sh),
233 (s, br). X-ray quality single crystals were grown by slow diffusion of
dithyl ether into an acetone solution of the compound.

(8) Reaction of FeC12 and NH4CI.

An acetone solution (15 mL) of NH4Cl (0.127 g, 2.367 mmol) was

added to an acetone solution (15 mL) of FeC12 (0.300 g, 2.367 mmol), and

151

the reaction solution was stirred for 12 h. The resulting solution was
filtered through Celite to give a yellow filtrate and the solvent was removed
by evaporation under vacuum to give a pale yellow solid. The solid was
redissolved in MeOH, then filtered through Celite to yield a pale yellow
filtrate. After concentration of the pale yellow filtrate, followed by slow
precipitation with Et20, an off-white compound was obtained (yield: 0.375
g). IR (Nujol, cm’l): 3384 (s, br), 3137 (m, br), 2721 (w), 2466 (w), 1734
(w, br), 1405 (m), 1370 (s), 1106 (m), 1025 (s), 668 (w); v(FeCI) 462 (m,
br), 383 (m, br), 352 (m, br).

(9) Preparation of [PPh4]2[Fe2(u-O)Cl6] (31).

An acetone solution of [PPh4]2[Fe2Cl6] (0.119 g, 0.119 mmol) was
purged with 02 gas at -15 °C for 5 min, which resulted in a color change
from yellow to orange after 1 min. The reaction solution was stirred under
an 02 atmosphere for 30 min and the solvent was removed by evaporation
under vacuum. Et20 was added to precipitate a yellow solid, which was
washed with Et20 and dried under vacuum. (yield: 0.097 g, 80% based on
FeC12). IR (Nujol, cm‘l): 1585 (w), 1482 (w), 1339 (w), 1313 (w), 1260
(w), 1185 (w), 1164 (w), 1104 (3, br) 1027 (w), 997 (m), 756 (m) 746 (w,
sh), 720 (s), 687 (s), 618 (w), 527 (s, br); v(Fe—O—Fe) 874 (s, br), 466 (vw),
460 (vw); v(FeCl) 362 (s, br), 318 (m).

(10) Preparation of [Et4N]2[Fe2(u-O)C16] (32).

An acetone solution of [Et4N]2[Fe2Cl6] (0.100 g, 0.171 mmol) was
purged with Oz gas at -15 °C for 5 min, which resulted in an immediate
color change from yellow to orange. The reaction solution was stirred
under an Oz atmosphere for 30 min, and the solvent was removed by
evaporation under vacuum. Et20 was added to precipitate a yellow solid,
which was washed with Et20 and dried under vacuum. (yield: 0.094 g, 90%

152

basexl on FeC12). IR (Nujol, cm'l): 1597 (w), 1486 (s), 1393 (s), 1308 (w),
1186 (w), 1172 (s), 1069 (w) 1055 (mw), 999 (s, br), 783 (s); v(Fe-O—Fe)
858 (s, br), 464 (vw), 428 (w); v(FeCl) 345 (s, hr), 308 (m).

(11) Reactions of A2[Fe2Cl6] with Nitrogen Donors (A = PPh4 and

Et4N).

(1) Preparation of Fe2C14(2,2'-bpym)3 (34).

(a) Reaction of [PPh4]2[Fe2C16] with 2,2'-bpym. Single crystals
of 34 were grown by a slow diffusion of a MeOH solution of
[PPh4]2[Fe2Cl6] into a THF solution of 2,2'-bpym.

(b) Reaction of FeC12 with 2,2'-bpym. An acetone solution (15
mL) of 2,2'-bpym (0.075 g, 0.473 mmol) was added to an acetone solution
(15 mL) of FeC12 (0.040 g, 0.316 mmol), which resulted in an immediate
color change from pale brown to dark gray. The reaction solution was
stirred for 12 h to yield an orangish-red solution and a dark gray precipitate.
The former was discarded via cannula techniques, while the latter was
washed with MeOH, acetone, followed by Et20 and dried in vacuo to give
a dark gray compound (yield: 0.053 g, 46% based on FeC12). Anal. Calcd
for Fe2C14N12C24H13: C, 39.60; H, 2.49; N, 23.09. Found: C, 35.72; H,
2.06; N, 20.44. IR (Nujol, cm'l): 1588 (w), 1572 (m), 1555 (mw, br), 1404
(s), 1140 (vw), 1018 (vw), 1006 (vw), 834 (w), 827 (w), 761 (mw), 753
(w), 686 (mw), 658 (mw); v(FeCl) 302 (vw), 265 (w, sh), 253 (m), 227 (w,
br). ueff= 6.9 113 at 300 K (0.1T).

(ii) Preparation of [Et4N]Cl-Fe2Cl4(l\'IeOH)4(u-2,2'-bpym) (35).

Reaction of [Et4N]2[Fe2Cl6] and 2,2'-bpym. Single dark brownish
green crystals of 35 were grown at the interface by a slow diffusion of a
MeOH solution of [Et4N]2[Fe2Cl6] into a THF solution of 2,2'-bpym.

153

(iii) Preparation of FeClz(2,2‘-bpy) (36).

Reactions of A2[Fe2Cl6] with 2,2'-bpy (A = PPh4 and Et4N). A
mixture of 2,2'-bpy (0.080 g, 0.512 mmol) and [Et4N]2[Fe2Cl6] (0.150 g,
0.256 mmol) was dissolved in 15 mL of acetone, which resulted in an
immediate color change from pale yellow to red. The reaction solution was
stirred for 12 h to yield an almost colorless solution and a cherry-red
precipitate. The former was discarded via cannula techniques, while the
latter was washed with MeOH and acetone, followed by EtzO and dried in
vacuo to give a dark gray compound (yield: 0.152 g, 68% and 0.142 g, 72%
for Et4N and PPh4 respectively). IR (Et4N, Nujol, cm'l): 1603 (w), 1579
(vw), 1311 (vw), 1183 (w), 1079 (w, br), 1033 (w), 798 (w), 768 (ms), 733
(m), 285 (8, br). IR (PPh4, Nujol, cm'l): 1604 (w), 1583 (w), 1443 (s),
1439 (sh), 1313 (w), 1261 (w), 1162 (w), 1107 (s), 1031 (w), 995 (w), 802
(w), 761 (m, br), 724 (s), 688 (m), 534 (m, sh), 527 (s), 281 (s), 265 (sh).

(iv) Reaction of A2[Fe2Cl6] with 4,4'-bpy (A = PPh4 and Et4N).

A mixture of 4,4'-bpy and A2[Fe2Cl6] (A = PPh4 and Et4N) were
loaded in a Schlenk flask in a molar ratio of 2:1 and dissolved in 15 mL of
acetone, which resulted in an immediate color change from pale yellow to
red. The reaction solution was stirred for 12 h to yield an almost colorless
solution and an orange precipitate. The former was discarded via cannula
techniques, while the latter was washed with acetone to remove any
unreacted starting material, followed by Et20 and dried in vacuo to give an
orange compound (yield: 0.098 g and 0.115 g based on 0.150 g of FeC12 for
PPh4 and Et4N respectively). IR (PPh4, Nujol, cm" 1): 1605 (ms), 1583 (w),
1533 (w), 1492 (w), 1415 (m), 1222 (m), 1107 (ms, br), 1080 (mw), 1048
(w), 1008 (mw), 995 (mw, br), 859 (w), 811 (s), 761 (111, hr), 720 (s), 688
(ms), 633 (ms), 563 (w), 527 (s, br), 498 (m), 445 (w); v(FeCl) 393 (w),

154

281 (m), 262 (m, sh), 250 (m), 216 (m). IR (Et4N, Nujol, cm'l): 1620 (w),
1605 (ms), 1534 (mw), 1492 (mw), 1415 (m), 1309 (w), 1222 (m), 1183
(w), 1080 (m), 1048 (mw), 1033 (w), 1006 (m), 867 (w), 811 (s), 730 (m,
br), 633 (s), 563 (mw), 496 (m); v(FeCl) 393 (w), 282 (m), 249 (m), 216
(m).

(12) Preparation of F e4Cl3(THF )6 (33).

An amount of FeC12 (1.00 g, 7.89 mmol) was dissoved in 40 mL of
THF and refluxed for 12 h. An off-white precipitate was obtained along
with a brown solution, which was removed via cannula techniques. The
off-white precipitate was washed with THF, followed by Et20, and dried in
vacuo to give an off-white compound, Fe4C13(THF)6 (yield: 1.436 g, 78 %
based on FeC12). Anal. Calcd for Fe4ClgO6C24H43: C, 30.68 %; H, 5.15 %.
Found: C, 30.28 %; H, 4.98 %. IR (Nujol, cm'l): 1299 (w), 1249 (w), 1180
(w), 1025 (vs), 919 (ms), 874 (vs/br), 674 (w); v(FeCl), 335 (s), 294 (m),
254 (8). “eff: 11.2 1113 at 300K (0.1T).

(13) Reactions of F e4Cls (THEM with nitrogen donors.

(i) Reaction of F e4Cls(THF)6 with one equiv. of 2,2-bpym. An
acetone solution (10 mL) of one equivalent of 2,2'-bpym (0.034 g, 0.212
mmol) was added to an acetone solution (15 mL) of Fe4Clg(THF)5 (0.200
g, 0.212 mmol), which resulted in an immediate color change from pale
yellow to a cloudy grayish-black with a purplish-black precipitate. The
reaction solution was stirred for 12 h to yield a colorless supernatant (which
was discarded via cannula techniques) and a dark precipitate, which was
washed with acetone, followed with Et20, and dried under vacuum to give
0.078 g of a dark solid. The solid is insoluble in all common organic
solvents except DMA, DMF, and water. IR (Nujol, cm'l): 1676 (w), 1620
(w, br), 1576 (ms), 1563 (m, sh), 1411 (ms), 1338 (w), 1306 (vw), 1280

155

(vw), 1252 (vw), 1216 (w), 1145 (vw), 1100 (w), 1069 (w), 1027 (mw), 835
(mw, br), 761 (s), 668 (mw) 673 (s), 390 (vw), 321 (vw), 272 (m), 244 (m,
br).

(ii) Reaction of F e4Cls(THF)6 with two equiv. of 2,2-bpym. An
acetonitrile solution (6 mL) of two equivalents of 2,2'-bpym (0.034 g, 0.212
mmol) was added to an acetonitrile solution (10 mL) of Fe4C13(THF)6
(0.100 g, 0.106 mmol), which resulted in an immediate color change from
clear pale yellow to cloudy grayish-black with a purplish—black precipitate.
The reaction solution was stirred for 12 h to yield a colorless supernatant
(which was discarded via cannula techniques) and a dark precipitate, which
was washed with acetonitrile, followed by Et20, and finally dried under
vacuum to give 0.055 g of a dark solid. The solid is insoluble in all
common organic solvents except DMA, DMF, and water. IR (Nujol, cm'l):
1641 (vw), 1621 (vw), 1602 (vw), 1576 (s), 1563 (m, sh), 1411 (s), 1338
(w), 1306 (vw), 1280 (vw), 1252 (vw), 1216 (w), 1145 (vw), 1100 (w),
1069 (w), 1027 (w), 835 (mw, br), 761 (m), 668 (w) 673 (mw), 272 (m),
244 (m, br).

(iii) Reaction of Fe4Cl3(THF)6 with two equiv. of 2,2-bpy. An
acetone solution (5 mL) of two equivalents of 2,2'-bpy (0.050 g, 0.320
mmol) was added to an acetone solution (10 mL) of Fe4C13(THF)6 (0.150
g, 0.160 mmol), which resulted in an immediate color change from clear
pale yellow to cloudy orange. The reaction solution was stirred for 12 h to
yield a pale orange supernatant (which was discarded via cannula
techniques) and an orange precipitate, which was washed with a small
amount of acetone, followed with Et20, and finally dried under vacuum to

give 0.101 g of an orange solid. The solid is slightly soluble in acetone,
CH3CN, and CHzClz, and moderately soluble in CH3N02 and MeOH to

156

give red solutions. IR (Nujol, cm‘l): 1688 (ms), 1679 (m, sh), 1604 (m, sh),
1597 (ms), 1574 (w), 1563 (w), 1491 (w), 1442 (s, br), 1317 (mw), 1250
(mw), 1171 (mw), 1160 (w), 1090 (w, br), 1057 (w), 1020 (m), 1012 (w,
sh), 979 (w), 906 (w), 818 (w), 776 (vs), 734 (s), 652 (mw), 630 (w), 545
(w), 419 (mw), 360 (vw), 324 (m, br), 251 (m, hr), 233 (m, br).

(iv) Reaction of Fe4Cls(THF )6 with an excess of 4,4'-bpy. An
acetone solution (10 mL) of excess 4,4'-bpy (0.080 g, 0.512 mmol) was
added to an acetone solution (15 mL) of Fe4C13(THF)6 (0.100 g, 0.106
mmol), which resulted in an immediate color change from clear pale yellow
to cloudy orange. The reaction solution was stirred for 12 h to yield a
nearly colorless supernatant which was discarded via cannula techniques.
The orange precipitate was washed with acetone followed with Et20, and
dried under reduced pressure to give an orange solid of 0.120 g. The solid
is insoluble in all common organic solvents except DMA, DMF, and water.
IR (Nujol, cm‘l): 3059 (w), 1700 (w, br), 1604 (s), 1533 (w), 1492 (mw),
1415 (s), 1261 (w), 1222 (ms), 1080 (m), 1048 (m), 1008 (mw), 857 (w),
812 (s), 730 (w), 668 (vw), 632(ms), 566 (w), 499 (mw), 393 (m), 286 (w),
250 (s).

(14) Preparation of [Mn(2,2'-bpym)2][BF4]2 (37).

A mixture of [Mn(NCCH3)4][BF4]2 (0.100 g, 0.255 mmol) and two
equivalents of 2,2‘—bpym (0.081 g, 0.510 mmol) was dissolved in 15 mL of
acetone and stirred for 12 h to give a pale yellow precipitate. The former
was discarded via cannula techniques, while the latter was washed with an
additional quantity of acetone (20 mL) to remove any unreacted starting
material, followed by Et20, and then dried under reduced pressure to yield
pale yellow compound (yield: 0.097 g, 70%). Anal. Calcd for MnN3C16-
H12B2F3: C, 35.27; H, 2.22; N, 20.57. Found: C, 33.70; H, 1.89; N, 19.35.

157

IR (Nujol, cm'l): 3090 (w, br), 1707 (w), 1592 (w, sh), 1574 (s), 1556 (m),
1410 (s), 1286 (w), 1058 (s, br), 1006 (m), 992 (w), 822 (w, hr), 762 (s),
690 (ms), 656 (ms), 521 (w); v(FeN) 238 (ms).

(15) Reaction of F e4Cls(THF )6 with [Mn(2,2'-bpym)2][BF4]2

A mixture of [Mn(2,2'-bpym)2][BF4]2 (0.070 g, 0.128 mmol) and
Fe4C13(THF)6 (0.120 g, 0.128 mmol) was loaded in a Schlenk flask in a
molar ratio of 1:1 and dissolved in 15 mL of acetone, which resulted in the
instantaneous formation of cloudy dark solution. The reaction solution was
stirred for 12 h to yield a nearly colorless solution and a dark precipitate.
The former was discarded via cannula techniques, while the latter was
washed with acetone to remove any unreacted starting materials, followed
by Et20, and finally dried in vacuo to yield a dark solid (yield: 0.151 g). IR
(Nujol, cm'l):1577 (s), 1406 (s), 1219 (vw), 1095 (w), 1056 (m, br), 1026
(sh), 823 (w), 754 (m), 689 (w), 671 (w), 521 (vw), 271 (m).

(16) Preparation of Mn4Cls(THF )6 (38).

An amount of MnClz (0.500 g, 3.973 mmol) was dissoved in 30 mL
of THF and refluxed for 12 h. The resulting off-white precipitate was
collected by filtration, washed with THF followed by Et20, and dried in
vacuo to give a white solid (yield: 0.765 g, 82 % based on MnClz). Anal.
Calcd for Mn4C1306C24H43: C, 30.80 %; H, 5.17 %; Cl, 30.30 %. Found:
C, 30.83 %; H, 5.20 %; Cl, 29.83 %. IR (Nujol, cm"1): 1369 (mw), 1345
(vw), 1261 (w), 1172 (vw), 1035 (8, hr), 918 (mw), 885 (m ,br), 799 (vw),
675 (w).

(17) Preparation of [H-TMPP]2[C02C16] (39).

A mixture of [H-TMPP]C1 (0.369 g, 0.210 mmol) and CoClz (0.048

g, 0.369 mmol) was dissolved in 15 mL of acetone to give a blue solution

which was stirred for 12 h after which time a blue solid was observed to

158

have formed. The blue solution was filtered through Celite and the
precipitate was washed with acetone (30 mL) which was filtered through
Celite and combined with the original filtrate. After concentration of the
acetone solution, a blue compound was harvested by addition of Et20
(yield: 0.171 g, 66% based on CoClz). IR (Nujol, cm'l): 1712 (w), 1593
(s), 1577 (s), 1432 (mw), 1413 (ms), 1338 (ms), 1230 (s), 1206 (s), 1183
(w), 1162 (m), 1136 (s), 1114 (m), 1103 (m), 1094 (m, sh), 1025 (m), 950
(w), 929 (mw), 915 (w), 906 (w), 884 (w), 826 (mw), 817 (m), 802 (vw),
789 (w), 676 (vw), 645 (vw); v(FeCl) 353 (s, br), 311 (m), 261 (m), 243
(m). yeti: 5.5 1113 at 300 K (1 T).
(18) Preparation of [H-TMPP]2[Mn2C16] (40).

A mixture of [H-TMPP]C1 (0.360 g, 0.205 mmol) and MnClz (0.046
g, 0.360 mmol) was dissolved in 15 mL of acetone and the reaction solution
was stirred for 12 h to yield a white precipitate and a colorless solution.
The colorless solution was filtered through Celite and the precipitate was
washed with acetone (15 mL) which was filtered through Celite and
combined with the original filtrate. After concentration of the filtrate
followed by slow precipitation with Et20, an off-white compound was
obtained (yield: 0.160 g, 64% based on MnClz). IR (Nujol, cm‘l): 1712
(w), 1593 (s), 1577 (s), 1432 (mw), 1413 (ms), 1339 (ms), 1230 (s), 1204
(s), 1183 (w), 1162 (m), 1136 (s), 1114 (m), 1103 (m), 1094 (m, sh), 1025
(m), 949 (w), 929 (mw), 915 (w), 907 (w), 885 (w), 826 (mw), 817 (m), 803
(vw), 790 (w), 676 (vw), 645 (vw), 522 (w), 476 (mw), 429 (mw), 409
(mw); v(FeCl) 342 (8, br), 292 (m), 248' (m), 227 (m). “eff = 7.1 “B at 300
K (1 T).

159

C. X-ray Crystallographic Studies

Crystallographic data for compounds 25, 26, 28, 30, and 31 were
collected on a Rigaku AFC6S diffractometer, and data for 27, 34, 35, 36,
37, and 39 were collected on a Nicolet P3N diffractometer; both are
equipped with monochromated Mo K01 radiation. A 2 KW sealed tube
generator was used for the former, while a 3 KW sealed tube generator was
for the latter. Crystallographic computing was performed on a
VAXSTATION 4000 by using the Texsan crystallographic software
package of Molecular Structure Corporation.10 Crystal parameters and
basic information pertaining to data collection and structure refinement are
summarized in Table 4.1 (25, 26, 27, and 28), Table 4.6 (30), Table 4.9 (34,
35 and 36), Table 4.11 (33), Table 4.13 (37) and Table 4.15 (39).
(1) [PPh4]2[Fe2CI6] (25). Single crystals of 25 were grown by a slow
diffusion of hexanes into an acetone solution of the title compound. A pale
yellow crystal of dimensions 0.62 x 0.89 x 0.62 mm3 was secured on the tip
of a glass fiber with Dow Corning silicone grease and placed in a cold
N2(g) stream. Least-squares refinement using 23 well—centered reflections
in the range 34.3 S 20 _<_ 38.2° defined a triclinic crystal system. The data
were collected at - 100 i 1 °C using the 00-20 scan technique to a maximum
20 value of 50°. A total of 4246 reflections were collected, 3988 of which
were unique. An empirical absorption correction based on azimuthal scans
of three reflections was applied which resulted in transmission factors
ranging from 0.89 to 1.00 and the data were corrected for Lorentz and
polarization effects. The structure was solved by PHASE”, followed by
DIRDIF12 and refined by full-matrix least-squares refinement. All non-
hydrogen atoms were refined anisotropically. The final full-matrix
refinement was based on 3491 observed reflections with F02> 30(F02) that

160

were used to fit 342 parameters to give R = 0.027 and Rw = 0.043. The
goodness-of-fit index was 2.06, and the highest peak in the final difference
map was 0.40 e‘/A3.

(2) [Et4N]2[Fe2Cl6] (26). Single crystals of 26 were grown by a slow
diffusion of hexanes into an acetone solution of the title compound. A pale
yellow crystal of dimensions 0.67 x 0.45 x 0.37 mm3 was secured on the tip
of a glass fiber with Dow Corning silicone grease and placed in a cold
N2(g) stream. Least—squares refinement using 17 well-centered reflections
in the range 39.5 _<_ 20 S 399° indicated that the crystal belonged to the
monoclinic crystal system. The data were collected at - 100 i 1 °C using
the 00-20 scan technique to a maximum 20 value of 50°. Of the 2686
reflections that were collected, 2513 were unique. An empirical absorption
correction based on azimuthal scans of three reflections was applied which
resulted in transmission factors ranging from 0.81 to 1.00. The data were
corrected for Lorentz and polarization effects. The space group was
determined to be P21/n based on the observed systematic absences. The
structure was solved by PHASE11 and followed by DIRDIF12 structure
solution programs and refined by full-matrix least-squares refinement. All
non-hydrogen atoms were refined anisotropically. The final full-matrix
refinement was based on 1926 observed reflections with F02> 30(F02) that
were used to fit 198 parameters to give R = 0.027 and Rw = 0.038. The
goodness-of-fit index was 1.68, and the highest peak in the final difference
map was 0.34 e‘lA3.

(3) [ppnlszezClg] (27). Single crystals of 27 were grown by a slow
diffusion of diethyl other into a methanol solution of the title compound. A
pale yellow crystal of dimensions 0.26 x 0.34 x 0.29 mm3 was secured on

the tip of a glass fiber with Dow Corning silicone grease and placed in a

161

cold N2(g) stream. Least-squares refinement using 39 well-centered
reflections in the range 5.5 _<_ 20 S 23.3° indicated a monoclinic crystal
system. Data were collected at - 85 + 1 °C using the 00-20 scan technique to
a maximum 20 value of 47° and were corrected for Lorentz and polarization
effects. Of the 10685 reflections that were collected, 10353 were unique.
An empirical absorption correction based on azimuthal scans of three
reflections was applied which resulted in transmission factors ranging from
0.80 to 1.00. The structure was solved by MITHRIL13 and DIRDIF12
structure solution programs and refined by full-matrix least-squares
refinement. All non-hydrogen atoms were refined anisotropically except
for atom N2 and some ring carbons of the [ppn] + ion due to the lack of data.
The final full-matrix refinement was based on 3890 observed reflections
with F 02> 30(F02) that were used to fit 630 parameters to give R = 0.080
and Rw = 0.080. The goodness-of-fit index was 2.94, and the highest peak
in the final difference map was 0.80 e‘/A3.

(4) [AsPh4]2[Fe2Cla] (28). Single crystals of 28 were grown by a slow
diffusion of hexanes into an acetone solution of the title compound. A pale
yellow crystal of dimensions 0.52 x 0.21 x 0.39 mm3 was secured on the tip
of a glass fiber with Dow Corning silicone grease and placed in a cold
N2(g) stream at - 100 i 1 °C. Least-squares refinement using 13 well-
centered reflections in the range 39.4 S 20 S 40.0° indicated that the crystal
belonged to a triclinic crystal system. The (1)-20 scan technique was used to
collect data to a maximum 20 value of 47°, which give 3402 unique
reflections out of a total of 3632. An empirical absorption correction based
on azimuthal scans of three reflections was applied which resulted in
transmission factors ranging from 0.79 to 1.00. The data were corrected for
Lorentz and polarization effects. The structure was solved by PHASE11

162

and followed by DIRDIF12 structure solution programs in the P-l space
group and refined by full-matrix least—squares refinement. All non-
hydrogen atoms were refined anisotropically. The final full-matrix
refinement was based on 2682 observed reflections with F02> 30(F02) that
were used to fit 342 parameters to give R = 0.027 and Rw = 0.035. The
goodness-of-fit index was 1.50, and the highest peak in the final difference
map was 0.28 e'/A3.

(5) [BzNEt3]2[FeCl4] (30). Single crystals of 30 were grown from a
solution of [BzNEt3]2[Fe2Cl6] dissolved in Et20 and CH3CN at 0 °C. A
pale yellow crystal of dimensions 0.49 x 0.52 x 0.39 mm3 was secured on
the tip of a glass fiber with Dow Corning silicone grease and placed in a
cold N2(g) stream. Least-squares refinement using 21 well-centered
reflections in the range 34.5 S 20 S 39.2° indicated that the crystal belonged
to the monoclinic crystal system. Data were collected at - 100 i 1 °C using
the 00-20 scan technique to a maximum 20 value of 47°. A total of 4794
reflections were gathered, of which 4599 were unique. The data were
corrected for Lorentz and polarization effects and an empirical absorption
correction based on azimuthal scans of three reflections applied to the data
resulted in transmission factors ranging from 0.91 to 1.00. The space group
was determined to be P21/c based on the observed systematic absences.
The structure was solved by MITHRIL13 and developed with the use of the
DIRDIF12 structure solution programs. All non-hydrogen atoms were
refined anisotropically. The final full-matrix refinement was based on 3054
observed reflections with F 02> 30(F02) that were used to fit 298
parameters to give R = 0.031 and Rw = 0.048. The goodness-of-fit index
was 1.84, and the highest peak in the final difference map was 0.30 e'lA3.

163

(6) Fe4Cls(THF)6 (33). Single crystals of 33 were grown by a slow
diffusion of hexanes into a solution of acetone and THF (1/4) of the title
compound. A pale yellow crystal of dimensions 0.62 x 0.40 x 0.31 mm3
was secured on the tip of a glass fiber with Dow Corning silicone grease
and placed in a cold N2(g) stream. Least-squares refinement using 12 well-
centered reflections in the range 39.6 S 20 S 39.8° indicated that the crystal
belonged to the triclinic_crystal system. The data were collected at - 100 +
1 °C using the (1)-20 scan technique to a maximum 20 value of 50°. Of the
3508 reflections that were collected, 3308 were unique. An empirical
absorption correction based on azimuthal scans of three reflections was
applied which resulted in transmission factors ranging from 0.87 to 1.00.
The data were corrected for Lorentz and polarization effects. The structure
was solved by MITHRIL13, followed by DIRDIF12 structure solution
programs and refined by full-matrix least-squares refinement with all non-

hydrogen atoms being treated anisotropically. The final refinement was
based on 2844 observed reflections with F 02> 30(F02) that were used to fit

214 parameters to give R = 0.033 and Rw = 0.047. The goodness-of-fit
index was 2.22, and the highest peak in the final difference map was 0.86 e'
/A3.

(7) Fe2C14(2,2'-bpym)3 (34). Single crystals of 34 were grown by slow
diffusion of a MeOH solution of [PPh4]2[Fe2CI6] into a THF solution of
2,2'-bpym. A dark crystal of dimensions 0.18 x 0.26 x 0.21 mm3 was
secured on the tip of a glass fiber with Dow Corning silicone grease and
placed in a cold N2(g) stream. Least-squares refinement using 25 well-
centered reflections in the range 15.4 S 20 S 26.2° indicated the triclinic
crystal system. Data were collected at - 84 i 1 °C using the 00-20 scan

technique to a maximum 20 value of 47°. The data, which were corrected

164

for Lorentz and polarization effects, included 2272 reflections, 2078 of
which were unique. An empirical absorption correction based on azimuthal
scans of three reflections was applied which resulted in transmission factors
ranging from 0.84 to 1.00. The space group was determined to be P-l . The
structure was solved by MITHRIL13 and DIRDIF12 structure solution
programs and refined by full-matrix least-squares refinement with all non-
hydrogen atoms being refined anisotropically. The final refinement cycle
was based on 1598 observed reflections with F 02> 30(F02) that were used
to fit 226 parameters to give R = 0.032 (Rw = 0.038) and a goodness-of-fit
index of 1.38; the highest peak in the final difference map was 0.45 e‘/A3.
(8) [Et4N]CI-[Fe2Cl4(MeOH)4(p-2,2'-bpym)I (35). Single crystals of 35
were grown by a slow diffusion of a MeOH solution of [PPh4]2[Fe2C16]
into a THF solution of 2,2'-bpym. A dark crystal of dimensions 0.16 x 0.18
x 0.44 mm3 was secured on the tip of a glass fiber with Dow Corning
silicone grease and placed in a cold N2(g) stream. Least-squares refinement
using 26 well-centered reflections in the range 15.6 S 20 S 27.1° indicated
that the crystal belonged to a monoclinic crystal system. The data were
collected at - 80 i 1 °C using the 00-20 scan technique to a maximum 20
value of 47°. Structure factors have not been fully refined due to problems
in the low angle data.

(9) F eClz(2,2'-bpy) (36). Single crystals of 36 were grown by slow
diffusion of hexanes into a methanol solution of the products obtained from
the reactions of A2[Fe2C16] with 2,2'-bpy (A = PPh4 and Et4N). A red
crystal of approximate dimensions 0.47 x 0.26 x 0.29 mm3 was secured on
the tip of a glass fiber with Dow Corning silicone grease and placed in a
cold N2(g) stream. Least-squares refinement using 24 well-centered

reflections in the range 20.1 S 20 S 31 .4° indicated that the crystal belonged

165

to the monoclinic crystal system. Data were collected at - 100 + 1 °C using
the (1)-20 scan technique to a maximum 20 value of 50°. Of the 1008
reflections that were collected, 974 were unique. The data were corrected
for Lorentz and polarization effects and an empirical absorption correction
based on azimuthal scans of three reflections was applied which resulted in
transmission factors ranging from 0.91 to 1.00. The space group was
determined to be C2/c based on the observed systematic absences. The
structure was solved by MITHRIL13 and DIRDIF12 structure solution
programs and refined by full-matrix least-squares refinement. All non-
hydrogen atoms were defined anisotropically in the final least squares cycle
which was based on 637 observed reflections with F 02> 30(F02) that were
used to fit 85 parameters to give R = 0.022 and Rw = 0.028. The goodness-
of-fit index was 1.22 and the highest peak in the final difference map was
0.34 e‘lA3.

(10) [Mn(2,2'-bpym)2(H20)2][BF4]2-20120) . Single crystals of the title
compound were grown by slow evaporation of a H20 solution of [Mn(2,2'-
bpym)2]BF4]2 (37). A colorless crystal of dimensions 0.26 x 0.29 x 0.26
mm3 was secured on the tip of a glass fiber with Dow Corning silicone
grease and placed in a cold N2(g) stream. Least-squares refinement using
24 well-centered reflections in the range 15.2 S 20 S 25.8° indicated that the
crystal belonged to the monoclinic crystal system. Data were collected at -
83 i 1 °C using the (1)-20 scan technique to a maximum 20 value of 47°. Of
the 1973 reflections that were collected, 1920 were unique. An empirical
absorption correction based on azimuthal scans of three reflections was
applied which resulted in transmission factors ranging from 0.78 to 1.00.
The data were corrected for Lorentz and polarization effects. The space

group was determined to be C2/c based on the observed systematic

166

absences. The structure was solved by MITHRIL13 and DIRDIF12
structure solution programs and refined by full-matrix least-squares
refinement. All non-hydrogen atoms were refined anisotropically. The
final full-matrix refinement was based on 1115 observed reflections with
F 02> 30(F02) that were used to fit 177 parameters to give R = 0.046 and
Rw = 0.052. The goodness-of-fit index was 1.61, and the highest peak in
the final difference map was 0.56e-/A3.

(11) [H-TMPP]2[C02C16] (39). Single crystals of 39 were grown by slow
diffusion of hexanes into an acetone solution of the title compound. A blue
crystal of dimensions 0.26 x 0.31 x 0.29 mm3 was secured on the tip of a
glass fiber with Dow Corning silicone grease and placed in a cold N2(g)
stream. Least-squares refinement using 25 well-centered reflections in the
range 12.8 S 20 S 24.4° indicated that the crystal belonged to the
monoclinic crystal system. Data were collected at - 85 i 1 °C using the to-
20 scan technique to a maximum 20 value of 47°. Of the 5181 reflections
that were collected, 4959 were unique. An empirical absorption correction
based on azimuthal scans of three reflections was applied which resulted in
transmission factors ranging from 0.76 to 1.00. The data were corrected for
Lorentz and polarization effects. The structure was solved in the space
group P21/n by MITHRIL13 and followed by DIRDIF12 structure solution
programs and refined by full-matrix least-squares refinement. All non-
hydrogen atoms were refined anisotropically expected for atom C7. The
final full-matrix refinement was based on 2865 observed reflections with
F 02> 30(F02) that were used to fit 365 parameters to give R = 0.063 and
Rw = 0.068. The goodness-of-fit index was 2.09, and the highest peak in
the final difference map was 0.90 e'IA3.

167

3. Results and Discussion
A. Chemistry of [F e2Cl6]2' and [Fe2(u-0)C16]2'.

(1) Syntheses. The [H-TMPP]+ salt of [Fe2Cl4]2', 24, was first
synthesized in our laboratories from the unexpected reduction of ferric
chloride (FeCl3) by the highly basic tertiary phosphine (T MPP = tris(2,4,6-
trimethoxyphenyl)phosphine).33 The purity and yields for this method were
not satisfactory, however, thus 24, as well as a series of related ferrous
chloride A2[Fe2Cl6] salts, was later synthesized by a rational route that
involves reactions of ferrous chloride FeC12 with various salts AC1 (A = H-
TMPP (24), PPh4 (25), Et4N (26), ppn (27), AsPh4 (28) and BzNEt3 (29))
in a molar ratio of 1:1. The diferrous salts are all hygroscopic and air-
sensitive, with the larger cations producing more stable compounds. The
off-white dinuclear anion species decomposes into the mononuclear
tetrachloroferrate anion [FeCl4]2' in coordinating solvents such as CH3CN
and MeOH, as demonstrated by the formation of [BzNEt3]2[FeCl4] (30)
from a solution of [BzNEt3]2[Fe2Cl6] (29) in CH3CN/Et20. The oxo—
bridged dinuclear [Fe2(u-O)C16]7-‘ salts were obtained from exposure of
compounds 25 or 26 to 02 or air.

(2) Molecular Structures of 25-28 and 30. The compound [H-
TMPP]2[Fe2Cl6] (24) was fully characterized in our laboratories several
years ago,3 thus only pertinent structural data are included for comparison
purposes to the new salts in the series. ORTEP drawings and selected bond
distances and bond angles are presented in Figure 4.1 and Table 4.2 for 25,
Figure 4.2 and Table 4.3 for 26, Figure 4.3 and Table 4.4 for 27, and Figure
4.4 and Table 4.5 for 28. The geometry of the [Fe2C16]2' core in all the salts
is of D211 symmetry (Figure 4.1) which is in accord with the pattern of the
stretching vibrations v(FeCl) (vas, vs, ring) observed in the far-IR region.

168

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170

 

 

 

 

 

Table 4.2. Selected bond distances (A) and bond angles (°) for
[PPh4]2[F62Cl6] (25).

Bond Distances
A B A-B (A) A B A-B (A)
Fel Fe1* 3.4517(9) P1 C1 1.793(2)
Fel C11 2.2653 (9) P1 C7 1.799(2)
Fel C12 2.4048 (8) P1 C13 1.796(2)
Fel C12* 2.4021 (9) P1 C19 1.791 (2)
Fel C13 2.2540 (8)

Bond Angles

A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C12 110.01 (3) C1 P1 C7 111.0(1)
C11 Fel C12* 112.16 (3) C1 P1 C13 106.4(1)
C11 Fel C13 118.86 (3) C1 P1 C19 110.3(1)
C12 Fel Cl2* 88.21 (3) C7 P1 C13 110.7 (1)
C12 Fel C13 110.95 (3) C7 P1 C19 106.4 (1)
Fel C12 Fel* 91.79 (3) C13 P1 C19 112.0(1)

 

171

 

Figure 42. ORTEP drawing of [Et4N]2[Fe2Cl6] (26).

172

Table 4.3. Selected bond distances (A) and bond angles (°) for
[Et4N]2[FezCl6] (26).

 

 

 

 

 

Bond Distances
A B A-B (A) A B A-B (A)
Fel Fe1* 3.4232(9) N1 C1 1.517(3)
Fel C11 2.252 (1) N1 C3 1.525 (3)
Fel C12 . 2.392(1) N1 C5 1.518(3)
Fel C12* 2.4027 (9) N1 C7 1.522(3)
Fel C13 2.2440(9)

Bond Angles

A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C13 116.74 (4) C1 N1 C3 108.3 (2)
C11 Fel C12 110.53 (4) C1 N1 C5 111.3 (2)
C11 Fel C12* 112.33 (3) C1 N1 C7 108.4 (2)
C13 Fel C12 113.27 (3) C3 N1 C5 108.9 (2)
C13 Fel C12* 111.83 (3) C3 N 1 C7 111.2 (2)
C12 Fel Cl2* 88.88 (3) C5 N1 C7 108.8 (2)
Fel C12 Fe1* 91.12 (3)

 

173

 

Figure 4.3. ORTEP drawing of [ppn]2[Fe2Cl(5] (27).

Table

174

4.4. Selected bond distances (A) and bond angles (0) for
[Ppn]2[F62Cl6] (27).

Bond Distances

 

 

 

 

A B A-B (A) A B A-B (A) A B A-B (A)
Fel Fe1* 3.452(6) Fe2 Fe2* 3.353(6) N1 P1 1.61 (1)
Fel C11 2.239(6) F62 C14 2.235(6) N1 P2 159(1)
Fel C12 2.418(5) F62 C15 2.399(6) N1 P3 1.60(1)
Fel C12* 2.387(6) F62 C15* 2.388(6) N1 P4 159(1)
Fel C13 2.252(6) F62 C16 2.256(6)

Bond Angles
A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C13 120.0 (2) C14 F62 C16 119.82 (2)
C11 Fel C12 109.5 (2) C14 F62 C15 105.3 (2)
C11 Fel C12* 110.4 (2) C14 F62 C15* 114.5 (2)
C13 Fel C12 110.7 (2) C16 Fe2 C15 115.5 (2)
C13 Fel C12* 113.5 (2) C16 F62 C15* 107.2 (2)
C12 Fel C12* 88.2 (2) C15 F62 C15* 91.1 (2)
Fel C12 Fe1* 91.8 (2) F62 C15 Fe2* 88.9 (2)
P1 N1 P2 134 (1) P3 N2 P4 139 (1)

 

175

 

Figure 4.4. ORTEP drawing of [AsPh4]2[Fe2C16] (28).

Table 4.5. Selected bond distances (A) and bond angles (°) for

176

 

 

 

 

 

[AsPh4]2[F62C16] (28)-

Bond Distances
A B A-B (A) A B A-B (A)
Fel Fel* 3.431 (1) Asl C1 1.914(4)
Fel C11 2.263 (1) Asl C7 1.916(4)
Fel C12 2.404(1) Asl C13 1.915(4)
Fel C12* 2.402(1) Asl C19 1.905 (4)
Fel C13 2.256 (1)

Bond Angles

A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C12 109.28 (5) C1 Asl C7 110.8 (2)
C11 Fel C12* 112.25 (5) C1 Asl C13 106.6(2)
C11 Fel C13 119.52 (5) C1 Asl C19 109.9 (2)
C12 Fel C12* 88.88 (4) C7 Asl C13 111.1 (2)
C12 Fel C13 110.48 (5) C7 Asl C19 106.4(2)
Fel C12 Fe1* 91.12 (4) C13 Asl C19 112.1 (2)

 

177

The average distances of Fe-Cl(terminal) ligands are between 2.235 and
2.265 A for 24—28,3 which is intermediate between distances found in Fen-
CI (2.25-2.35 A) for [FeCl4]2‘ compounds14 and Fem-Cl (2.15-2.20 A) for
[FeCl4]' compounds”. The bridging angles of L Fe-Cleridging)—Fe are in
the range of 88.64 (8) - 91.8 (2) °, which are relatively small deviations
from tetrahedral geometry. In the case of the ppn+ salt, it is worth noting
that there are two types of [FezClslz' anions observed in the solid state with
the very different bridging Fe-Cl-Fe angles of 91.8(2)° and 88.9 (2)°. In the
series, [H-TMPP]2[Fe2Cl(,] exhibits the most acute bridging angle, while
one of the [ppn]2[Fe2Cl6] molecules exhibits the highest obtuse angle.
Three-dimensional packing diagrams of 25-28 presented in Figures 4.5-4.8,
respectively, depict the relationship of the cation to the packing
arrangements of the [Fe2Cl6]2' anion as well as their intermolecular
contacts. The shortest contacts between the terminal chlorides of two
adjacent [Fe2C16]2‘ anions are in the range of 5.584 (3)-6.642 (2) A for 25-
28. Structural diversity is also observed in the way the columns of dimers
are arranged, with parallel arrangements observed for 25 and 28, and zigzag
arrangements observed for 26 and 27. These structural patterns are
important in determining the antiferromagnetic exchange coupling between
dimers which manifests itself in different maximum effective magnetic
moments (see Section A3).

The identity of [BzNEt3]2[Fe2C16] (29) was confirmed by IR
spectroscopy and elemental analysis. Attempts to grow single crystals
suitable for X-ray analysis by slow diffusion of Et20 into an acetone
solution of 29 at r.t. (which is a reliable methode for growing single crystals
of salts of the type A2[Fe2Cl6]), yielded the decomposition product
[BzNEt3]2[FeCl4] (30). Compound 30 was also obtained from a solution of

178

 

.8826 a 65 as... 8.6; as Eosaafig B 889.6 ”56.8.. .3. 6.53...

 

 

 

179

 

 

 

 

 

 

 

 

 

Figure 4.6. Packing diagram of [Et4N]2[Fe2Cl6] (26) viewed along the c

direction.

 

181

 

 

Figure 4.8. Packing diagram of [AsPh4]2[FezC16] (28) viewed along the b direction.

182

Table 4.6. Summary of crystallographic data for [BzNEt3]2[FeCl4] (30).

 

 

compound [BzNEt3]2[FeCl4] (30)
formula FeCl4N2C26H44
formula wt 582.31

space group P21/c

a, A 15.016 (4)

b, A 11.542 (2)

c, A 17.269 (2)

(1, deg 90

6, deg 100.76 (1)

y, deg 90

v, A3 2940(1)

Z 4

dclac, g/cm3 1.315

n, cm-1 8.95

temp, °C -100 :l: 1

Ra 0.031

W) 0.048

 

a R = XIIFoI - IFcll/ZIFoI. b Rw = [ZWlFoI - ch|)2/ZWIF6|2]1’2; W = 1/02(|Fo|)-

183

 

C11

C1 0
C11

F01
012 OK!

C14

 

Figure 4.9. ORTEP drawing of [BzNEt3]2[FeCl4] (3o).

184

 

 

 

 

 

Table 4.7. Selected bond distances (A) and bond angles (°) for
[BzNEt3]2[FeCl4] (30).
Bond Distances

A B A-B (A) A B A-B (A) A B A-B (A)

Fel C11 2.322(1) N1 C3 1.513(5) N2 C16 1.516(5)

Fel C12 2.323 (1) N1 C5 1.507 (5) N2 C18 1.518(5)

Fel C13 2.343 (1) N1 C7 1.545 (5) N2 C20 1.535 (5)

Fel C14 2.334(1) C7 C8 1.506(6) C20 C21 1.512 (6)

N1 C1 1.523 (6) N2 C14 1.522 (5)

Bond Angles

A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C12 119.61 (5) C1 N1 C5 110.9 (3)
C11 Fel C13 103.83 (5) C1 N1 C7 106.5 (3)
C11 Fel C14 103.41 (5) N1 C7 C8 115.0(4)
C12 Fel C13 102.27 (5) C14 N2 C16 111.4(3)
C12 Fel C14 109.00 (5) C14 N2 C18 106.4 (3)
C13 Fel C14 119.62 (5) C14 N2 C20 111.0(3)
Cl N1 C3 1 11.0 (3) N2 C20 C21 116.7 (3)

 

185

[BzNEt3]2[Fe2Cl6] (29) in CH3CN and Et20. An ORTEP drawing as well
as selected bond distances and bond angles of 30 are presented in Figure 4.9
and Table 4.7, respectively. The Fe—Cl bond distances are in the range of
2.322 (1)-2.343 (1) A, which is longer than that reported for Fe(II)-Cl.14
The Cl—Fe-Cl'bond angles in the range of 102.27 (5)-119.62 (5)°, are nearly
ideal. It was noted that compound 30 is not among the reported [FeCl4]2-
salts in the literature.

(3) Magnetic Studies of 24—28. SQUID measurements of the
[Fe2Cl6]2' salts reveal interesting behavior indicative of ferromagnetically
coupled S=2 metal centers. Temperature-dependent SQUID measurements
of 24—29 were performed in the range of 2-300 K at 0.05T(Tesla), in the
range 4—300 K at ST and at 0.1T. Reduced magnetization studies of 24—29
were performed in the range of 2-4 K at 0.05T, 1T, 2T, and 4T, while the
temperature range 2-300 K was employed for 5T data. Due to the large
number of data collected that revealed analogous behaviors, only
representative plots are depicted herein. Plots of )(m and me vs
temperature at 5T, [Jeff vs temperature at 5T, reduced magnetization vs HIT
(field/temperature) and reduced magnetization vs H (field) respectively for
[H-TMPP]2[Fe2Cl6] (24) are presented in Figures 4.10 (a,b) and 4.11 (a,b).
The effective magnetic moment (ueff)16 for 24 at 300 K (Figure 4.10b) is
approaching 8.1 1113, which is much higher than the value expected for two
non-coupled high-spin Fe(II) atoms (ueff = 6.9 1113), but is close to the
theoretical value for two ferromagnetically coupled Fe(II) centers (ueff =
8.9 m3). No saturation was achieved even at a field strength of 5 Tesla
(Figure 4.11a). This is supported by the reduced magnetization vs field plot
in Figure 4.11b, where it can be observed that the reduced magnetization is

still rising and approaching 3.9, which is much smaller than the expected

(a)

XIII

(b)

ueff

186

 

 

 

 

 

 

 

 

 

 

 

 

 

04 . 1 4 l J l l J l 1 l L l 9
0.35 5‘ v v ' 8
. . v v
1 v '
0.3 f: . V v V 7
: v'
025—; o'v'" ' Xmfl 6
: ><
0.2 '3 vv. 5 a
0.15 -: V O 4
: o
0.1-f 0,... . Xm 3
0.05 4' '
iv . . . . . O O o
O I I I I I I I I I I T I I I I I I I I I I I I I I I I I _IT1
0 50 100 150 200 250 300
T (K)
9 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I
1
8: . . . . g C
- o
75 00.... . :
2 O I
: o '
6:- . :-
: 0 E
55 8 L
:o E
. .
4 . _-
3 I I I I I I I I I r I I I I I I I I I I I I I I I I I I I .
0 50 100 150 200 250 300
T (K)

Figure 4.10. Plots of (a) )(m and me vs the absolute temperature and (b)

the effective moment vs the absolute temperature at 5T for

[H-TMPP]2[Fe2C15] (24).

187

 

 

 

 

 

 

 

 

(a) 4 .1 I J I I I II I IJ I4 J
5 o . . C
3.5“ o . -
I O I
3.: 0 I;
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2.‘ ' ' 5 T :_
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1.5“: ' 2 T r
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1 I I I I r Ij r17 I rt I I I rI r I I I I r1 I .-
0 5000 10000 15000 20000 25000 30000
HIT
I L I I I I I I I I I I I I I
(b) 4 3 o :
3.5'5 o E‘
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13750 27500 41250 55000
H (gauss)

Figure 4.11. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced magnetization vs

the magnetic field for [H-TMPP]2[Fe2C16] (24).

188

value (8 for an S=4 ground state). A possible spin ladder for [Fe2Cl6]2'
salts with a ground state of S=4 is shown in Scheme 4.1, in which a large
perturbation of zero-field splitting is shown along with Zeeman effects.
The true ground state for this type of compound can only be obtained by a
combination of very strong field strengths and low temperature to yield a
well separated ground state and excited state, and to avoid any thermal
population from the ground state to the first excited state (Scheme 4.1). We
evidently did not achieve this in our laboratories.

The magnetic behavior of the [Fe2C16]2' salt 25 (A+ = [PPh4]+) is
presented in Figures 4.12 (a,b) and 4.13 (a,b). For the [PPh4]+ salt, the
effective magnetic moment at room temperature is lower than that of [H-
TMPP]+, but increases with decreasing temperature; furthermore the
reduced magnetization is much higher (at 5 Tesla and 2 K the value is 6.6
as shown in Figure 4.13a). Similar behavior was observed for
[ppn]2[Fe2Cl6] (27) as shown in Figures 4.14 (a,b) and 4.15 (a,b), but with
a lower effective magnetic moment and a smaller reduced magnetization
being observed. The effective magnetic moment of 25 is only slightly
affected by the field, thus it is not likely that different states are being
populated for the fields ranging from 0.1T to ST. The plot of ueff vs
temperature increases and reaches a maximum of ~8.0 1.13 at 20K before
zero-field splitting and intermolecular antiferromagnetic coupling effects
become dominant (Figure 4.12b).

A third example of the behavior of the [Fe2Cl6]2‘ salt 26 (A+ =
[Et4N]+) is presented in Figures 4.16 (a,b) and 4.17 (a,b). For the [Et4N]+
salt, the effective magnetic moment at room temperature is also lower than
that of [H-TMPPl‘“, but increases very slightly with decreasing temperature

at a field strength of 5 Tesla; furthermore the reduced magnetization is

1

189

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0 50 100 150 200 250 300
T (K)

Figure 4.12. Plots of (a) )(m and )(mT vs the absolute temperature and (b)
the effective moment vs the absolute temperature at 5T for [PPh4]2[Fe2Cl6]

(25).

191

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(a) 7 '
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1 . 0 0.05 T :_
O I I I I I I I I I III I I I I ' I I I I I I I I I h
0 5000 10000 15000 20000 25000
HIT
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(b) I Q . t
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0 13750 27500 41250 55000
H (gauss)

Figure 4.13. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (Hfl') and (b) reduced magnetization vs
the magnetic field for [PPh4]2[Fe2C16] (25).

192

 

 

 

 

 

 

 

 

 

 

 

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(a) {'vv v
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0.1 ' 5
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0 I I I I I I I I I I l I I I I I I I I I l I I.I I? 005
50 100 150 200 250 300
T (K)
I l I I I I I I I j I I I I I I I I I I I I I I
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=- L
205 l T I I I l I I I I I I I I I l I I I I l I I I I I I I I I b
0 50 100 150 200 250 300

T (K)

Figure 4.14. Plots of (a) )(m and )(mT vs the absolute temperature and (b)
the effective moment vs the absolute temperature at 5T for [ppn]2[Fe2C16]

(27) .

193

 

 

 

 

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0 13750 27500 41250 55000
H (gauss)

Figure 4.15. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HIT) and (b) reduced magnetization vs

the magnetic field for [ppn]2[Fe2Cl6] (27).

194

much higher (at 5 Tesla and 2K the value is 5.4 as shown in Figure 4.17a).
In fact, the effective magnetic moment remains relatively constant at 0.1
Tesla with decreasing temperature before zero-field splitting and
intermolecular antiferromagnetic coupling effects evidently become
dominant. It can be seen that the effective magnetic moment of 26 is
virtually field-independent. The plot of [Jeff vs temperature increases only
slightly and reaches maximum of ~7.3 “B at 60K (Figure 4.16b). Similar
behavior was observed for [AsPh4]2[Fe2Cl6] (28), as shown in Figures 4.18
(a,b) and 4.19 (a,b). The plot of peff vs temperature increases very slightly
and reaches a maximum of ~7.4 LIB at 40K (Figure 4.18b). The reduced
magnetization is still rising and approaching 5.6 (Figure 4.19a), which is
very close to the value observed for [Et4N]2[Fe2Cl6].

Preliminary fittings of the molar magnetic susceptibility data for
[PPh4]2[Fe2Cl6] and [Et4N]2[Fe2Cl6] by a simple Heisenberg spin
Hamiltonian equation (H = 418182),” excluding zero-field splitting
parameters the magnitude of which we have not determined, reveal small
negative I values. The existence of large zero-field splitting for this system
is supported by the non-superimposability of the magnetization data
measured at various fixed fields as shown in the plots of reduced
magnetization vs HIT (field/temperature).13 These results support the
conclusion that large zero-field splitting (D) parameters for these diferrous
(11) ions play an important role at low temperatures, and are therefore
seriously complicating the overall spin ladder, and thereby rendering the
application of a simplified isotropic Heisenberg fitting unjustified. In fact it
may even be the case that J and D are of a similar magnitude. In addition,
intermolecular contacts that produce weak anti-ferromagnetic couplings are

obviously playing an important role at low temperature, with packing

(a)
0.5

0.4

XIII

0.3

0.2

0.1

0

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(b)

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195

 

 

 

 

 

 

 

 

 

 

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0 50 100 150 200 250 300
1'00

lmx

Figure 4.16. Plots of (a) )(m and XmT vs the absolute temperature and (b)

the effective moment vs the absolute temperature at 5T for [Et4N]2[Fe2C16]

(26).

(a)

M/NB

(b)

M/NB

196

 

 

 

 

 

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H (gauss)

Figure 4.17. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (H/I') and (b) reduced magnetization vs

the magnetic field for [Et4N]2[Fe2C16] (26).

197

 

 

 

 

 

 

 

 

 

 

 

 

 

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0 50 100 150 200 250 300
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0 50 100 150 200 250 300

T (K)

Figure 4.18. Plots of (a) Xm and me vs the absolute temperature and (b)
the effective moment vs the absolute temperature at 5T for [AsPh4]2[Fe2C16]

(28).

M/Nfi

M5

198

 

 

 

 

 

 

 

 

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5.5 o o o o a ._
: ° :
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35 . I" I ' _
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o I I I I l I I I I l I T I I I I If' I I I I I b
0 5000 10000 15000 20000 25000
HIT
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o I I I l I I I I I I I I I I r -
0 13750 27500 41250 55000
H (gauss)

Figure 4.19. Plots of (a) reduced magnetization vs the ratio of magnetic
field over the absolute temperature (HfI') and (b) reduced magnetization vs

the magnetic field for [AsPh4]2[Fe2C16] (28).

199

influences being responsible for mediating these magnetic effects. The
most relevant parameters that can be gleaned from the solid state structures
are the Fe-Cl-Fe bridge angle (which is directly related to intramolecular
superexchange) and the shortest Cl ----- Cl contacts between nearest neighbor
[Fe2C16]2‘ units which mediates intermolecular contacts; both are important
in terms of the overall magnetic behavior. Fittings must be accomplished
with the use of more detailed expressions for the Hamiltonian that take into
account the effects of (D) and J ' intermolecular antiferromagnetic
couplings. A summary of structural parameters and maximum magnetic
moments for the series A2[Fe2C16] (A = H-TMPP (24), PPh4 (25), Et4N
(26), ppn (27), and AsPh4 (28)) is presented in Table 4.8). A maximum
neff (~ 8.1 113) was obtained for 24 with the Fe-Cl-Fe bridging angle less
than 90°, while a similar magnitude of neff (7.25-7.4 1113) was obtained for
25, 26, and 28 with bridging angles in the range of 91.1-91.8°. The
complexity of the magnetic properties for this system is further supported
by the dissimilar effective magnetic moments observed for compounds 26
and 28, which possess identical Fe-Cl-Fe bridging angles.

(4) Reactions of A2[Fe2Cl6] with 02 (A = PPh4 (25), Et4N (26):

Preparation of A2[Fe2(u-O)C16] (A = PPh4 (31), Et4N (32).

The compound FeCl3(O=TMPP) was prepared from the reaction of
[H-TMPP]2[Fe2C15] with 02 in our laboratories.3b The intermediate in this
reaction is thought to be a dinuclear bridging-0x0 compound with an [H-
TMPP]+ counter ion, but this was not verified, because intermediates with
[H-TMPPP salt were too unstable to be isolated. Due to our considerable
interest in the magnetism and reactivity of [Fe2C16]2', we were curious as to
the nature of its decomposition products, especially with 02, if no other

reason than to be aware of its identity and know how to avoid it. The

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cations [PPh4]+ and [Et4N]+ were employed to prepare A2[Fe2(u-O)Cl6] (A
= PPh4 (31) and Et4N (32)) from the reactions of A2[Fe2Cl6] with 02 in
acetone at ~15 °C as orangish-brown solids. The identities of these two
compounds were confirmed by comparing their IR spectroscopic data to the
data for the authentic compounds reported in the literature for a sample
prepared by a different route.19 The salt [Et4N]2[Fe2(u-O)Cl6] has been
reported by Lippard et al., while [PPh4]2[Fe2(u-O)Cl6] was included in the
study by Wieghardt et al. who further examined the magnetic properties of
a series of [Fe2(u-O)Cl6]2' salts.19 These results are in accord with our
compounds prepared from the ferrous salt and support the contention that
our samples of [Fe2C1612‘ are not contaminated with [Fe2(u-O)C16]2‘.

B. Reactions of A2[Fe2Cl6] with Nitrogen Donors (A = PPh4 (25), Et4N

(26)).

The nitrogen donors 2,2'-bipyridine (2,2'-bpy), 4,4'-bipyridine (4,4'-
bpy), and 2,2'-bipyrimidine (2,2'-bpym) were reacted with A2[Fe2Cl6] (A =
PPh4 and Et4N) to investigate the potential coordination sites of the
diferrous salts [Fe2C16]2' and further to explore the possibility of preparing
polymeric structures with cooperative interactions. The [Fe2C16]2‘ core
appears to cleave in many of these reactions as evidenced by the isolation
and stuctural characterization of Fe2C14(2,2'-bpym)3 (34) (from the reaction
of [PPh4]2[Fe2C16] with 2,2'-bpym), which possesses antiferromagnetically
coupled Fe(II) centers. Two related compounds (Fe2(NSC)4(2,2'-
bpym)3203 and C02(NSC)4(2,2'-bpym)320b) have been recently reported
and also exhibit antiferromagnetic coupling behavior.

An ORTEP drawing as well as selected bond distances and bond
angles for Fe2C14(2,2'-bpym)3 are presented in Figure 4.20 and Table 4.10.
The average Fe-Cl bond distance is 2.40 A, which is longer than the

202

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Figure 4.20. ORTEP drawing of Fe2C14(2,2'-bpym)3 (34).

Table 4.10.
F62C14(2,2'-bpym)3 (34).

204

Selected bond distances (A) and bond angles (°) for

 

 

 

 

 

Bond Distances
A B A-B(A) A B A-B(A)
Fel Fe1* 5.918(2) Fel N6 2.271 (3)
Fel Cll 2.402(1) N1 C4 1.342(5)
Fel C12 2.391 (1) N2 C4 1.340(5)
Fel N1 2.208(3) N3 C5 1.351 (5)
Fe] N3 2.218 (3) N4 C5 1.328 (5)
Fel N5 2.224 (3) N5 C12 1.339 (5)
Bond Anglers

A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C12 102.77 (5) N1 Fel N3 74.7 (1)
C11 Fel N1 95.27 (9) N1 Fel N5 171.2(1)
C11 Fel N3 90.3 (1) N1 Fel N6 99.4 (1)
C11 Fel N5 91.51 (9) N3 Fel N5 99.7 (1)
C11 Fel N6 164.03 (8) N3 Fel N6 87.5 (1)
C12 Fel N3 162.35 (9) N5 Fel N6 73.3 (1)

 

205

corresponding distances reported for Fen-Cl of FeCl4 (225-2.35 A)14 and
Fem-Cl of FeCl4 (2.15-2.20 A)”. The Fe-N(terminal) bond distances are
2.208 (3) and 2.187 (3) A, which are somewhat similar to that reported for
Fe2(NSC)4(2,2'-bpym)3 (2.200 (6) and 2.211 (6) A) but are shorter than
those for (C02(NSC)4(2,2'-bpym)3 (2.161 (2) and 2.127 (2) A). The Fe-
N(bridging) bond distances of 2.224 (3) and 2.271 (3) A are shorter than
that reported for (Fe2(NSC)4(2,2'-bpym)3 (2.316 (6) A) but somewhat
similar to that observed for (C02(NSC)4(2,2'-bpym)3 (2.185 (2) and 2.279
(2) A). The separation between two intramolecular Fe(II) atoms is 5.918
(2) A, which is longer than the corresponding distance observed in
(Fe2(NSC)4(2,2'-bpym)3 (5.522 (6) A). Three dimensional packing
diagrams of 34 viewed down the b axis as well as along the c direction are
presented in Figures 4.21 and 4.22 respectively. The closest intermolecular
Fe ----- Fe contact is 7.047 (1) A, which is much shorter than the
corresponding distance reported for (Fe2(NSC)4(2,2'-bpym)3 (9.138 (2) A)
and clearly supports n-stacking of the 2,2'-bpym ligands. The fact that the
thiocyanate derivative does not exhibit close contacts between bpym rings
may be rationalized by the fact that the smaller ligand Cl‘ allows for a
closer separation between two molecules than does the larger NSC' ligand.
Plots of )(m and XmT vs temperature, ueff vs temperature at 0.1 T for
Fe2C14(2,2'-bpym)3 (34) are presented in Figures 4.23 (a, b) respectively.
The molar magnetic susceptibility increases with decreasing temperature
and reaches a maximum at 20 K (Figure 4.23a). The curve of XmT vs
temperature decreases continuously upon cooling and approaches zero as
the temperature approaches absolute zero (Figure 4.233). The appearance
of a maximum in the molar magnetic susceptibility curve is characteristic

for antiferromagnetically coupled paramagnetic centers.21 The value of

206

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b axis.

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the effective moment vs the absolute temperature at 0.1T for Fe2C14(2,2'-

bpym)3 (34)-

209

ueff16 at room temperature (300 K) is 6.8 113 (Figure 4.23b), which is very
close to the theoretical value for two non-interacting Fe(II) atoms (6.9 11B)-
The Néel temperatures as well as J values reported for those two related
compounds are 12 K with J = 4.1 cm”1 for (Fe2(NSC)4(2,2'—bpym)3 and
16.4 K with J = -6.20 cm"1 for C02(NSC)4(2,2'-bpym)3.20 Preliminary
fitting (Figure 4.24) for Fe2C14(2,2'-bpym)3 to the Heisenberg-Dirac-van
Vleck equation gave g = 2.16 and J = —2.29 cm'1 (assuming D << I).

The cleavage of the [Fe2C16]2' core was further observed for the
products [Et4N]Cl-Fe2Cl4(MeOH)4(u-2,2'-bpym) (35) (from the reaction of
[Et4N]2[Fe2C16] with 2,2'-bpym) and FeC12(2,2'-bpy) (36) (from the
reaction of A2[Fe2Cl6] (A = PPh4 and Et4N) with 2,2'—bpy) (Scheme 4.2).
Compound 35 consists of two Fe(II) atoms bonded to a bridging 2,2'-bpym
ligand with terminal chlorides and methanol ligands, while the chloride ion
of the [Et4N]Cl salt interacts through hydrogen bonds with the hydrogen
atom of the MeOH ligands to form an infinite chain as shown in Figure
4.25. The reaction of A2[Fe2Cl6] (A = PPh4 and Et4N) with 4,4'-bpy
appears to produce a polymeric product based on the preservation of the
stretching vibration pattern in the v(FeCl) region and the poor solubility of
this compound in common organic solvents.

C. Chemistry of F e4Cls(THF)6 (33).

(1) Synthesis and Molecular Structure of 33. Fe4C13(THF)5 (33)
was first structurally characterized by Bulychev et al. who obtained the
product from the reaction of FeCl3 and szReH in THF.53 The same
cluster was later reported by Cotton and coworkers who were searching for
a soluble, reactive form of FeC12 from a comproportionation reaction of
FeCl3 with metallic Fe in refluxing THF.5b We accidentally discovered yet
a third method which involves the aggregation of [Fe2Cl6]2‘ units in THF

210

 

 

 

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Figure 4.24. Plot of )(m vs the absolute temperature for Fe2C14(2,2'-bpym)3
(34) obtained from the experimental data and by fitting to the Heisenberg-

Dirac-Van Vleck equation ( assume D << J).

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213

with elimination of Cl‘. We then developed the rational preparation of 33,
now used in our laboratories, that involves refluxing a suspension of
anhydrous FeC12 in THF, a procedure that gives pure Fe4Clg(THF)6 in high
yield. An ORTEP drawing obtained from a structure performed in our
laboratories is shown in Figure 4.26, verifies the identity of the compound.
Selected bond distances and bond angles of Fe4C13(THF)6 are presented in
Table 4.12. It is interesting to note that structures for [Fe2Cl6]2' and
Fe4C13(THF)6 can be extracted as fragments from the layer structure of
FeC12 (Figure 4.27). By analogy, the preparation of di- and tetranuclear
compounds of [M2C1612' and M4C13(THF)6 can be achieved by simialr
routes from the compounds MC12 (M = Mn, Co, Ni) that are of the Cdlz
structural type as FeC12.

(2) Magnetic Properties of 33. Magnetic measurements of
Fe4C13(THF)6 in the temperature range of 79-294 K by the Faraday method
had previously been reported by Bulychev et al. with the results suggesting
an overall ferromagnetically coupled Fe(II) tetramer.5a We undertook a
more thorough investigation of the magnetism of this fascinating cluster,
with particular attention to the low temperature range and to field
dependence studies, our goal being to establish the true magnetic ground
state if possible. DC SQUID susceptibility measurements of 33 are depicted
in the plots of [Jeff16 vs temperature at 5T, reduced magnetization (MIN 6) vs
HIT (field/temperature) and reduced magnetization vs H(field) at 2K as
shown in Figure 4.28 (a-c). As can be observed from these data, the
effective magnetic moment approaches the theoretical value for four
ferromagnetically coupled Fe(II) atoms (18.9 1113). The transition observed
in the plot of M/NB vs H is characteristic of "metamagnetic" behavior, with

antiferromagnetic-like coupling being observed below 15000 gauss and

Table 4.11. Summary of crystallographic data for Fe4C13(THF)6 (33).

 

 

compound Fe4C13(THF)6
formula Fe4ClgC24O6H48
formula wt 939.67

space group P-l

a, A 10.449 (3)

b, A 10.893 (4)

c, A 9.939 (3)

01, deg 111.75 (2)

[5, deg 97.42 (3)

Y, deg 63.47 (2)

V, A3 939 (1)

Z 1

dclac, g/cm3 1.704

p, cm-1 21.25

temp, °C - 100 i 1

Ra 0.033

wa 0.047

 

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215

 

Figure 4.26. ORTEP drawing of Fe4Clg(THF)6 (33).

216

Table 4.12. Selected bond distances (A) and bond angles (°) for

 

 

 

 

 

Fe4C13(THF)6 (33).
Bond Distances
A B A-B (A) A B A-B (A)
Fel Fel* 6.209(1) Fel 01 2.136(2)
Fe2 Fe2* 3.615 (1) Fe2 Cll 2.459(1)
Fel Cll 2.354 (1) Fe2 02 2.139 (2)
Fel C12 2.261 (1) Fe2 03 2.111 (2)
Fel C13 2.371 (1) Fe2 C14 2.159(2)
Fel C14 2.682 (1) Fe2 Cl4* 2.502 (1)
Bond Angles
A B C A-B-C (°) A B C A-B-C (°)
C11 Fel C12 125.90 (5) C11 Fe2 C14 87.07 (4)
C11 Fel C13 110.21 (4) C11 Fe2 02 88.76 (8)
C12 Fel C13 123.22 (4) C11 Fe2 03 88.87 (7)
01 Fe] Cll 89.34 (8) C11 Fe2 C13* 176.80 (3)
01 Fel C12 94.02 (8) Fe2 Cl4 Fe2* 96.28 (4)
01 Fel C13 92.38 (7) C14 Fe2 Cl4* 83.72 (4)
Fel Cll Fe2 97.98 (5)

 

217

 

   
 
  
   

   

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Figure 4.27. Structures of [Fe2C16]2’ (top) and Fe4Clg(THF)6 (bottom) can

be extracted as fragments (circled with dash line) from the layer structure of
FeC12 with O as Fe, 5 as Cl, and O asTHF.

 

 

 

 

 

 

 

 

 

 

 

 

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ratio of magnetic field over the absolute temperature (Hfl') and (c) reduced

magnetization vs the magnetic field at 2K for Fe4Clg(THF)6 (33).

219

 

 

 

 

THE, THF THE, THF
M/ /
2 M2
/ \ K’: \
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M1 'M1' :—__ M1’2"’“Ml'
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SB=SZ+SZ';SZ=SZ'=2;SB=493929190
Sr=SA+SB;ST=8,7,6,5,4,3,2, 1,0

H = “J 1[51251125321423.412512's1'21'1313132'522‘52'2]
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I1212sT+1)a(sT)exp<-E<ST)/k'r)

Preliminary result : g = 2.14 ; J, = +1.1 ; J2 = +2.5 ; assume J3 = O
with data of T 2 30 K at 0.1 Tesla

Scheme 4.3. Equation for fitting an M4 cluster obtained from
the Kambé vector coupling method.

220

ferromagnetic-like coupling being observed above 15000 gauss. This
phenomenon is not unknown and has been observed for both inorganic 223,9
and organic compounds 210A The fact that the data (shown in the plot of
M/NB vs H/T (Figure 4.28 (b)) measured at different fixed fields are not
superimposed on each other is known to be due to effects of the zero-field
splitting.18

Preliminary fitting of the effective magnetic moments from an
equation derived in our laboratories using the Kambe vector coupling
method23 (outlined briefly in Scheme 4.3) for 33 reveal two small positive J
values (J1 = +1.1, Jz = +2.5, and g = 2.14 at 0.1 Tesla with T 2 30 K; J1 =
+1.3, 12 = +2.5, and g = 2.14 at 0.05 Tesla with T Z 30 K; J1 = +8.5, .12 =
+1.8, and g = 2.39 at 5 Tesla with T 2 40 K). Of course, this approach does
not include zero-field splitting parameters which, are large and should be
accounted for in a more SOphisticated treatment of the molecule.

(3) Reactions of F e4C13(THF)6 with Nitrogen Donors. Reactions
of the cluster Fe4C13(THF)6 with nitrogen donors such as 2,2'-bipyridine
(2,2'-bpy), 4,4'-bipyridine (4,4'-bpy), and 2,2'-bipyrimidine (2,2'—bpym) and
proposed structures of the reaction products are summarized in Scheme 4.4.
Our goal is to explore the possibility of preparing polymeric structures with
cooperative interactions. Due to the difficulty in formulating products of
these reactions, molar magnetic susceptibility is replaced by gram magnetic
susceptibility. Plots of Xg vs temperature and ng vs temperature at 0.1 T
for the product obtained from the reaction of Fe4C13(THF)6 with 2,2'-bpy
are presented in Figure 4.29 (a,b), respectively. Plots of xg vs temperature
and ng vs temperature for the product obtained from the reaction with 2,2'-
bpym are presented in Figure 4.30 (a,b), respectively. The value of ng
(Figure 4.29 (b)) slightly increases with decreasing temperature and reaches

221

1. Fe4C18(THF)6 + 2 (2,2'-bpy) ——> Fe4C18(THF)2(2,2'-bpy)2
2. 1312408011106 + 4,4‘-bpy ——> [Fe4Clg(THF)4(4,4'-bpy)y]x

3. FC4C18(THF)6 + 2,2'-bpym —'—" [Fe4C18(THF)2(292"-bpym)y]x

postulated structures :

,, .~ \
'- / N N
.. {Ho
_ N—
(cr) 1,,
"F6: 'Fé Fe
THF/ ‘C1’ ‘c1 ( W
C11,". ~ecu“ “4THF
Fe 'Fe 'F'
N. THF/ [C13 ‘Cl
/_ x_\ {Fe
N‘3 \N
{ H \

 

Scheme 4.4. Reactions of Fe4C18(THF)6 with nitrogen donors.

222

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Fe4C13(THF)6 with 2,2'-bpy.

(a)

223

 

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1'00

100 150 200 250 300 350

Figure 4.30. Plots of (a) Xg vs the absolute temperature and (b) ng vs the

absolute temperature at 0.1T for the product obtained from the reaction of
Fe4Clg(THF')6 with 2,2'-bpym.

224

a maximum at 40K for the 2,2-bpy reaction, while the value of ng (Figure
4.30 (b)) remains relatively constant with decreasing temperature before
60K for the 2,2~bpym reaction. SQUID measurements of the products
obtained from the reaction with 4,4'-bpy are currently under investigation.
Efforts to crystallize the products from the reactions with 2,2'-bpy, 4,4'-bpy
and 2,2'-bpym are in progress.

D. Preparation and Reactions of [Mn(2,2'-bpym)2] [BF4]2 (37).

(1) Synthesis. [Mn(2,2'-bpym)2][BF4]2 (37) was obtained from the
reaction of [Mn(CH3CN)4][BF4]2 with 2,2'-bpym in a molar ratio of 1:2 in
acetone. The compound is insoluble in acetone, CH2C12, and CH3CN,
moderately soluble in MeOH and CH3N02, and soluble in H20. X-ray
quality single crystals were obtained from slow evaporation of an aqueous
solution of the compound in air. Attempts to grow crystals of the compound
in other solvent(s) failed. Three related 3d transition metal compounds
([CU(2,2"bem)2(H2O)][PF6]2'2(H20), [CU(2,2'-bpym)2(H20)l[00412-
-2(H20), and Co(2,2'--bpym)2C12)731'c and one 4d transition metal compound
([Ru(2,2'-bpym)3][PF6]2-CH3CN)7d, have been structurally characterized
recently, while compounds of the type [M(2,2'-bpym)3]2+ (M = Fe, Co, Ni,
Cu) and M(2,2'-bpym)2Clz (M = Mn, Co, Ni, Cu) have also been
characterized based on elemetal analysis7f. It is interesting to note that the

bpym ligands exhibit a cis arrangement in these compounds.

(2) Molecular Structure of [Mn(2,2'-bpym)2(H20)2][BF 412-
-2(H20). An ORTEP drawing as well as selected bond distances and bond
angles of [Mn(2,2'-bpym)2(H20)2]2+ are shown in Figure 4.31 and Table
4.13. The Mn(II) atom exhibits a distorted octahedral geometry supported
by two mutually cis 2,2'-bpym ligands and two H20 molecules. The

distortion around the metal center can be rationalized in terms of the

225

Table 4.13. Summary of crystallographic data for [Mn(2,2'-bpym)2-

 

 

(H20)2][BF4]2-2(H20).

compound [Mn(2,2'-bpym)2(H20)2][BF4]2-2(H20)
formula MnC16N804H14BzF3
formula wt 610.88

space group C2/c

a, A 24.97 (1)

b, A 7.633 (2)

c, A 18.548 (7)

(1, deg 90

6. deg 137.75 (2)

y, deg 90

V, A3 2377 (4)

Z 4

dclac, g/cm3 1.707

p, cm-1 6.34

temp, °C - 83 i 2

Ra 0.046

wa 0.052

 

a R = leFol - chII/XIFoI- b Rw = [ZWIFol - IFc|)2/XWIFo|2]1’2; W = 1/02(|Fo|)-

226

'II

 

4 TEp 2 b m H 0 2+
2 )2] .
" py )2(
. g Of the cation [Mn(2,
drawm
. 931. OR
Figure

227

Table 4.14. Selected bond distances (A) and bond angles (°) for [Mn(2,2'-
bpym)2(H20)2l[BF4]2°2(H20).

 

 

 

 

 

Bond Distances
A B A-B (A) A B A-B (A)
Mnl N1 2.258 (5) N2 C4 1.327(7)
Mnl N3 2.263 (5) N3 C5 1.328(7)
Mnl 01 2.168 (4) N4 C5 1.350(7)
N1 C4 1.352 (7) C4 C5 1.488 (81

Bond Angles

A B C A-B-C (°) A B C A-B-C (°)
N1 Mnl N3 73.2 (2) Mnl N1 C4 116.5 (4)
N1 Mnl 01 88.6 (2) Mnl N3 C5 115.6(4)
N1 Mnl 01* 166.4(1) N1 Mnl N1* 101.0(2)
N3 Mnl 01 93.9 (2) N1 Mnl N3* 98.0 (2)
N3 Mnl 01* 96.2 (2) N3 Mnl N3* 166.4(2)
01 Mnl 01* 83.7 (2)

 

228

constrains imposed by the five-membered metallacyles defined by Mnl-
Nl-C4—C5-N3 (73.2 (2)°). The bond distance Mnl-01 of 2.168 (4) A is
longer than the corresponding distances found in [Cu(2,2'-bpym)2(H20)]—
[PF6]2-2H20 and [Cu(2,2'-bpym)2(H20)][C104]2-2H20 (1.982 (5) and
1.993 (4) A respectively)”,b The bond distances of Mnl-N1 and Mnl-N3
(2.258(5) and 2.263 (5) A respectively) are longer than the corresponding
distances found in the literature (1.993 (4)-2.167 (2) A).7

(3) Magnetic Properties of 37. SQUID measurements of [Mn(2,2'-
bpym)2][BF4]2 (37) were performed in range of 5-300 K at 0.1 Tesla. Plots
of xm and I/Xm vs temperature and neff vs temperature at 1T of 37 are
presented in Figure 4.32 (a,b), respectively. Compound 37 does not follow
Curie-Weiss behavior as expected for a mononuclear compound of Mn(II)
based on the observation of a nearly straight line in the plot of llxm vs
temperature (Figure 4.32 (a)). This may be due to the 7r stacking for 2,2'-
bpym ligands between layers, a question that can only be resolved by
obtaining a solid state structure of [Mn(2,2'-bpym)2][BF4]2. The effective
magnetic moment (300 K) of 37 is 5.5 “B, which is close to the theoretical
value for a high—spin S=2/5 center (5.8-6.0 1.113).”

(4) Reaction with Fe4Cl3(THF)6. Reactions of Fe4C13(THF)6 with
nitrogen donors proceed with retention of the cluster framework. In
addition to the organic nitrogen donors, the new inorganic "building block"
[Mn(2,2'-bpym)2][BF4]2 with unligated nitrogen donors available for
bridging to another metal was reacted with Fe4C13(THF)6 in an attempt to
form an extended structure that displays ferrimagnetic behavior (Scheme
4.5). Plots of Xg vs temperature and ng vs temperature of the product
obtained from this reaction are presented in Figure 4.33 (a,b), respectively.

The value of gram magnetic susceptibility increases slowly upon cooling

(a)

)(m

ueff

 

229

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1 I 1 1 1 L1 1 1 1 1 I x 1 1 ll 1 J 1 I 1 l 100
. I
-. . l/Xm] . "80
a. . "
0.2 —‘ 3 0 I
E o . ’ —60
0.15 —‘ ' o I Q
I 9 ’ - B
3 9 ~40
0.l — ‘ ’ '
I . o .
. O .9. '
0.05 -‘ .20... ' Xfl .‘ 2°
I 9 O
’0 . Q . . . . . . . . _
O I I I I I I I I I I I I I II I I I I I I I I r] I I I I I I I o
0 50 100 150 200 250 300 350
T (K)
6 l I I l I 1 I I l I I l l J. I l I I l I I 1 I I I I I l I l I l I
5.5% .....oooooo.....é_
I o E
5; 0 Z.
5 - ;
4.5? . 2'
: o E
41 o ‘
. o I
3.5 .‘o :.
$0 :
3 I I I I 1 I I I I I I I I I I I I I I I I I I I T I I I I I I I I I '-
O 50 100 150 200 250 300 350
T (K)

Figure 4.32. Plots of(a) xm and 1/xm vs the absolute temperature, and (b)
the effective magnetic moment vs the absolute temperature at IT for

[Mn(2,2'-bpym)2l[BF4]2 (37).

230

acetone, r.t.
Fe4C18(THF)6 + [Mn(2,2'-bpym)zl[BF4lz . . ’

1mmed1ate

reaction

 

{ [FC4C18(THF)2(2,2"bPY m)2Mn][BF4]2} x

postulated structure :

3
z,"

NI N N / N a,"
I .
N N N N “c"
N
V Ni,“- /

(2.2-bpym) w

Scheme 4.5. Reaction of Fe4C18(THF)6 with [Mn(2,2'-bpym)2][BF4]2
and a postulated structure for the product.

231

 

(a) 0_m05 1111111111iniiljxhiliiiilmiiiliiii

0.0004 -

l" .

0.0003 {

IIIIIIIII

IIIII

X3
0

0.0002 { 0

0.0001- .0.

1 '0

. .°°Oo
O IIIIIIII IIITITITIIIIIII

I I I I I I I I I I I
0 50 100 150 200 250 300 350
T (K)

IIIIITIIII

 

 

 

 

 

 

 

(b) l l l 111 l l I l l l l 1 [LJ 1 [1L1] 11L] 1J1] l l 1
0.015- ....OO..:’
1 _
.. C ..
1 I
[— 0.01 1 .—
52 : o :
1 I
0.005% 9 _—
2 0 I
0 II I I I I I I I rI I I1 I I rTrI I I I I I I IT I I I I I I I-
0 50 100 150 200 250 300 350

T (K)

Figure 4.33. Plots of (a) Xg vs the absolute temperature and (b) ng vs the
absolute temperature at IT for the product obtained from the reaction of
Fe4C18(THF)6 with [Mn(2,2'-bpym)2][BF4]2.

232

and reaches a maximum value at 30 K (Figure 4.33a), which indicates a
ferrimagnetically coupling process between ferromagnetic Fe4C13(THF)6
and [Mn(2,2'-bpym)2]2+.

E. Chemistry of [H-TMPPlszzChs] (M = C0 (39), Mn (40)).

(1) Synthesis. Due to the ferromagnetic coupling behavior
displayed by [H-TMPP]2[Fe2Cl6] (24), it is interesting to synthesize and
study the magnetic properties of analogous anions with paramagnetic
metals including Co(II) and high-spin Mn(II). [H-TMPP]2[M2C16] (M =
C0 (39), Mn (40)) were synthesized by a similar route as mentioned in
Section A that involves reactions of MC12 with [H-TMPP]C1.9 Four
complexes containing the [CozCle' moiety have been previously
structurally characterized but no magnetic studies of these compounds have
been studied.24 The [M2X6]2‘ salts containing various metals and halides
such as [Mn2X6]2' (X = Br, [)25 and [Fezl6]2' 26 have been also structurally
characterized. It was noted that the chloride derivative of Mn(II) is not
known. The identity of [H—TMPP]2[Mn2C16] (40) is based on IR spectral
results in the v(Mn-Cl) region.

(2) Molecular Structures of 39. An ORTEP drawing and selected
bond distances and angles for [H-TMPP]2[C02C16] (39) are presented in
Figure 4.34 and Table 4.16. The average Co-Cl(terminal) and average Co-
Cl(bridging) distances of 2.22 A and 2.34 A are comparable to the
corresponding distances reported in the literature (2.212 (3)-2.238 (6) A for
distances of Co-CIminal, while 2.329 (5)-2.386 (3) A for distances for C0-
C1bridging)-24 The C0 ----- Co distance of 3.195 (3) A is shorter than the
corresponding distances reported in the literrature (3.277 (6)-3.366 (3) A).26
The Col-C12-C01* and ClZ-Co-C12* angles of 85.88 (9) and 94.12 (9) ° are
considerably distorted from an ideal tertahedral geometry. A three

Table 4.15. Summary of crystallographic data for [H-TMPP]2[C02C16]

 

 

(39).

compound [H-TMPP]2[C02C16]
formula CozCl6P2C54018H66
formula wt 1397.65

space group P21/n

a, A 14.266 (4)

b, A 10.164 (3)

c, A 22.443 (7)

01, deg 90

6, deg 106.05 (2)

17, deg 90

V, A3 3127 (3)

Z 2

dciac. g/cm3 1.484

11, cm“1 9.03

temp, °C - 85 i 2

Ra 0.063

wa 0.068

 

a R = XIIFol - chll/XIFoI. b Rw = [ZWlFol - IFCDZIXWIFolzl 1’2; W = 1/02(|Fo|)-

234

C13

 

 

'0
-
3‘
3;
“ ‘.
t g! 9
‘
-¢
\
K
‘

Figure 4.34. ORTEP drawing of [H-TMPP]2[C02CI6] (39).

235

Table 4.16. Selected bond distances (A) and bond angles (°) for
[H-TMPP]2[C02C16] (39).

 

 

 

 

 

Bond Distances
A B A-B (A) A B A-B (A)
C01 (361* 3.195(3) P1 (:1 1.768(8)
C01 C11 2.217 93) Pl (:7 1.781 (8)
Col on 2.336 (3) P1 C13 1.784(8)
Col (:12* 2.353 (3) P1 H1 1.01
C01 C13 2.218 (3)

Bond Angles

A B c A-B-C (°) A B C A-B-C (°)
C11 C01 C12 109.42 (9) C1 P1 c7 115.9(4)
C11 C01 (212* 110.93 (9) C1 P1 C13 114.9(4)
C11 C01 C13 116.2(1) C1 P1 H1 102.72
C13 C01 02 111.4(1) C7 P1 C13 108.4(4)
C13 C01 C12* 112.5 (1) C7 P1 H1 109.39
(:12 C01 C12* 94.12 (9) C13 P1 H1 104.67
C01 C12 C01* 85.88 (9)

 

.8886 c 65 e38 836; an Eomcoafiazha .6 888% 832$ .34 2:5

Dan om
immewwyc

 

 

 

237

dimentional packing diagram of 39 (Figure 4.35) viewed down the b axis
illustrates the segregated arrangement of the [H-TMPP]+ and the [Co2Cl6]2'
units.

(3) Magnetic Properties of 39. Temperature-dependent SQUID
measurements of [H-TMPP]2[C02C16] (39) were performed in the range of
2-300 K at 0.05 T(Tesla) 1 T and 5 T. Reduced magnetization studies of 39
were performed in the range of 2-4 K at 0.05T, 1T, 2T, and 4T, while 2-300
K at 5T. Plots of xm and me vs temperature at 5T, “eff vs temperature at
5T, reduced magnetization vs Hfl‘ (field/temperature) and reduced
magnetization vs H (field) respectively for [H-TMPP]2[C02C15] (39) are
presented in Figures 4.36 (a,b) and 4.37 (a,b). The effective magnetic
moment (neff) for 39 at 300 K (Figure 4.36b) is approaching 5.5 1,113, which
is the expected value for two non-coupled high-spin Co(II) atoms (neff =
5.5 113) but is much smaller than the theoretical value for two
ferromagnetically coupled Co(II) centers (near: 6.9 113). No saturation was
achieved even at a field strength of 5 Tesla (Figure 4.37a). This is
supported by the reduced magnetization vs field plot in Figure 4.37b, where
the reduced magnetization is still rising and approaching 0.72.

F. Synthesis of Mn4Cl3(THF)5. Attempts to synthesize Mn4Clg(THF')6
were made by following a procedure similar to that used for the syntheses
of Fe4C13(THF)6 and C04C13(THF)623. Reaction of anhydrous MnCl2 in
refluxing THF yields a white material, which is formulated as
Mn4C13(THF)6 based on IR spectroscopy and elemental analysis. We note
that the mononuclear compound, MnI2(THF)3, was reported to be the result
of a similar reaction of MnI2 in THF.29 The formation of mononuclear a
THF iodide derivative of divalent transition metal complexes is also
common to the chemistry of FeI2.27 The failure of M12 (M = Mn, Fe) to

(a)

xm

(b)

peff

238

 

 

 

 

 

 

 

 

0.08 1 . . 1 1 1 1 1 . 1 . 1 1 4
v v V V V V E
0.07 v ' 3-3-5
v * E
0.06 v I ' 1"” I :’3
0.05 ' 52's
o :‘2
0.04 I Q :
o 51.5
0.03 . . . xm E1
. :
0.02 9 3
O . . . lit-0.5
0001 U I U U U U l U U U U l U U U 1 I U U U U l U U U UtU U U : O
50 100 150 200 250 300 350
T (K)
6 | l I I l I l I I I I l I I l I I I I I . l I I l l l l l l l I l I l
. . g O O O C :
5 o ' '-
9 I
. b
4 L
o I
o I
3 -
. l-
J I
2 8 '-
1 U U U U ' U U U U l U U U U I U U U U I U U U U l U U U U l U U U U .
0 50 1 00 1 50 200 250 300 350

T (K)

 

lmx

Figure 4.36. Plots of (a) Xm and XmT vs the absolute temperature and (b)

the effective moment vs the absolute temperature at IT for
[H-TMPP]2[Co2Cl6] (39).

239

 

 

 

 

 

 

 

 

(a) l l 1 I 1 I j

o ' ° ° :—

0 O O O E

C . . :-

0 5

0:1. ‘ V E-
2 vv V 3
s V =-
93 E

0 5r _—

fig 0 4T :

v 2T :_

8 1T :

O 0.05T E-

' ' I V ‘ I T I I F I I I I I I I I I I I I I I I r:
5000 10000 15000 20000 25000 30000

HIT

(b) '8‘ 1 1 1 1 I 1 1 1 1 I 1 1 1 1 I 1 1 1 1 I 1 1 1 1 I 1 1
07-5- » . . , _

0.6-i . . o :_

m. 0.5— o _
g 0.45 ' E_
0.3-f ' E_

E ' E

0.13 0 :_

C. E

I I U l U U U r l U U U U U U U I U U U U U
0 10000 20000 30000 40600 50000
H (gauss)

Figure 4.37. Plots of (a). reduced magnetization vs the ratio of magnetic
field over the absolute temperature (H/l') and (b) reduced magnetization vs

the magnetic field for [I-l-TMPP]2[C02C16] (39).

240

form a tetranuclear complex by refluxing in THF is understood in terms of
the larger size of iodide ion, which can not accomodate the short distances
involved in the cluster framework.

4. Summary.

Discrete forms of ferrous chloride exhibit large magnetic moments
indicative of intramolecular ferromagnetic coupling; detailed quantitative
fittings await determination of the zero-field splitting parameters from epr
data. Mossbauer data would also complement these studies and allow for a
complete picture of the magnetic inte1pretation. It is believed from
preliminary results, that these systems constitute promising precursors to
large ordered arrays with cooperative properties. In-depth analyses of the
structural and magnetic properties of such di- and tetranuclear molecules
will help build a foundation of understanding to bridge the gap between
small molecular units and extended structures built from them. Given the
unusual properties of the Fe(II) compound, the ferromagnetically coupled
cluster C04C13(THF)6 and the proposed analogue Mn4C13CTHF)6 are also

worth pursuing for the synthesis of polymeric frameworks.

241

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10.

11.

12.

13.

14.

15.

242

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I3, 5.

Preparation of [H-TMPP]C1: Addition of dilute HCl into a benzene
solution of TMPP resulted in an immediate precipitation of white
solid. The reaction mixture was stirred for 30 min at r. t. A white
solid ([H-TMPP]C1) was collected after filtration, which was washed
with diethyl ether and dried in vacuo in nearly quantitative yield.

TEXSAN-TEXRAY Structure Analysis Package, Molecular
Structure Corporation, 1985.

PHASE - Calbrese,]. C. - Patterson Heavy Atom Solution Extractor.
Univ. of Wisconsin - Madison, Ph. D. Thesis, 1972.

DIRDIF - Beurskens, P. T.-Direct Methods for Difference Structures;
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6525 Ed Nijmegen, Netherlands.

MITHRIL - Gilmore, C. J. J. Appl. Cryst. 1984, I7, 42, Univ. of
Glasgow, Scotland.

(a) Mason, R. McKenzie, E. D.; Robertson, G. B.; Rusholme, G. A.
Chem. Commun. 1968, 1673. (b) Freeman, H. C.; Milbum, G. H.
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A. Inorg. Chem 1975, 14, 348.

(a) Constant, G.; Daran, J. -C.; Jeannin, Y. J. Organomet. Chem.
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16.

17.

18.

19.

20.

21.

22.

23.
24.

25.
26.

27.

243

I4, 2467. (c) Glowiak, T.; Durcanska, E.; Ondrejkovicova, I.;
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-A. Acta Cryst. 1990, C46, 1424 and references therein.

“eff = 2.828(XmT)0-5; Xm = (EMU*fw)/(field*Mass in g) (fw =
formula weight)

0' Connor, C. J. Progr. Inorg. Chem. 1982, 29, 203 and references
therein.

Day, E. P. Methods in Enzymology, 1993, 227, 437 and references
therein.

Haselhorst, G.; Wieghardt, K.; Keller, 8.; Schrader, B. Inorg. Chem.
1993, 32, 520 and references therein.

(a) Real, A.; Zarembowitch, J.; Kahn, 0.; Solans, X. Inorg. Chem.
1987, 26, 2939. (b) De Munno, G.; Julve, M.; Lloret, F.; Faus, J.;
Caneschi, A. J. Chem. Soc. Dalton Trans. 1994, 1175.

For example: Mabbs, F. E. and Machin, D. J. Magnetism and
Transition Metal Complexes, John Wiley, New York, 1973.

(a) Willett, R. D.; Landee, C. P.; Gaura, R. M., Swank, D. D.;
Groenedijk, H. A.; van Duynevelt, A. J. J. Mag. Mag. Mater. 1980,
15-18, 1055. (b) Groenedijk, H. A.; van Duynevelt, A. J .; Blote, H.
W. J.; Gaura, R. M., Willett, R. D. Physica 1981, 1063, 47. (c)
Chouteau, G.; Veyret-Jeandey, C. J. Phys. (Paris) 1981, 42, 1441.
(d) Benoit, A.; Flouquet, J.; Gillon, B.; Schweitzer, J. J. Mag. Mag.
Mater. 1983, 31-34, 1155.

Kambe, K. J. Phys. Soc. Japan 1950, 5, 48.

(a) Harrison, W.; Trotter, J. J. Chem Soc. Dalton Trans. 1973, 61.
(b) Olson, W. L.; Dahl, L. F. Acta Cryst. 1986, C42, 541. (c)
Bulychev, B. M.; Kireeva, O. K.; Streltsova, N. R.; Belsky, V. K.;
Dunin, A. G. Polyhedron, 1992, 14, 1801.

(a) Pohl, S.; Saak, W.; Stolz, P. Z. Naturforsch. 1988, 43B, 171. (b)

Saak, W.; Haase, D.; Pohl, S. Z. Naturforsch. 1988, 43B, 289. (b)
Ruhlandt-Senge, K.; Miiller, U. Z. Naturforsch. 1992, 4 7B, 1075.

Saak, W.; Pohl, S. Z Anorg. Allg. Chem. 1987, 552, 186.

244

28. Sobota, P.; Olejnik, Z.; Utko, J .; Lis, T. Polyhedron 1993, 12, 613.
29. Stolz, P.; Pohl, S. Z. Naturforsch. 1988, 43B, 175.

APPENDIX

TABLES OF ATOMIC POSITIONAL PARAMETERS AND
EQUIVALENT ISOTROPIC DISPLACEMENT PARAMETERS

245

246

Table A.1. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
(TMPP)Mo(CO)4 (2).

 

 

atom x y z B(eq)
Mo(l) 0.16470(2) 0.30008(2) 0.73192(2) 1.87(l)
P(1) 0.37262(7) 0.31523(5) 0.73399(6) 1.66(3)
O(1) 0.1855(2) 0.3889(1) 0.6248(2) 2.2(1)
O(2) 0.6187(2) 0.2932(1) 0.8232(2) 2.7(1)
O(3) 0.6670(2) 0.5318(2) 0.9583(2) 3.1(1)
O(4) 0.3224(2) 0.4635(1) 0.7821(2) 2.4(1)
0(5) 0.5907(2) 0.0141(2) 0.7879(2) 3 .3(1)
0(6) 0.4194(2) 0.2311(1) 0.8880(2) 2.3(1)
O(7) 0.4315(2) 0.2068(2) 0.5856(2) 3.0(1)
O(8) 0.3597(2) 0.4590(2) 0.3812(2) 3.9(1)
O(9) 0.5642(2) 0.3359(2) 0.6333(2) 2.9(1)
O(10) 0.1715(3) 0.1727(2) 0.8698(2) 4.0(1)
O(1 1) 0.1204(3) 0.4113(2) 0.8860(2) 4.3(2)
C(30) 0.1692(3) 0.2220(2) 0.6358(3) 2.5(2)
O(12) 0.1632(3) 0.1776(2) 0.5817(2) 4.1(1)
C(31) 0.0035(3) 0.2876(3) 0.71 15(3) 3.0(2)
O(13) -0.0906(3) 0.2760(2) 0.7005(2) 5.3(2)
C( 1) 0.1102(4) 0.4501(3) 0.6072(3) 2.8(2)
C(2) 0.2805(3) 0.3915(2) 0.5830(2) 2.0(1)
C(3) 0.2768(3) 0.4254(2) 0.5023(2) 2.4(2)
C(4) 0.3716(3) 0.4259(2) 0.4619(2) 2.6(2)
C(5) 0.4703(3) 0.3956(2) 0.5030(3) 2.7(2)
C(6) 0.4713(3) 0.3634(2) 0.5857(2) 2.4(1)
C(7) 0.4674(3) 0.3766(2) 0.8051(2) 1 .9(1)
C(8) 0.5775(3) 0.3609(2) 0.8417(2) 2.0(1)
C(9) 0.6412(3) 0.4139(2) 0.8933(2) 2.4(2)
C(10) 0.5968(3) 0.4835(2) 0.9080(2) 2.3(2)
C(11) 0.4893(3) 0.5018(2) 0.8742(2) 2.2(1)
C(12) 0.4279(3) 0.4481(2) 0.8223(2) 1 .9(1)
C(13) 0.2740(4) 0.5337(2) 0.8013(3) 3.0(2)
C(14) 0.6299(5) 0.6072(3) 0.9663(3) 3 .6(2)
C(15) 0.7262(4) 0.2724(3) 0.8631(3) 3.2(2)
C(16) 0.4339(3) 0.2217(2) 0.7383(2) 1.9(1)
C(17) 0.4527(3) 0.1885(2) 0.8222(2) 1.9(1)
C(18) 0.5045(3) 0.1191(2) 0.8375(3) 2.3(1)
C(19) 0.5380(3) 0.0806(2) 0.7665(3) 2.5(2)

C(20)

0.5153(3)

0.1089(2)

0.6818(3)

2.6(2)

Table A.1. continued

atom

C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
H(l)

H(2)

H(3)

H(4)

H(5)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(l3)
H(14)
H(15)
H(16)
H( 17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)

X

0.4614(3)
0.4333(4)
0.4785(5)
0.6484(4)
0.4505(5)
0.3758(3)
0.6658(4)
0.1680(3)
0.1417(3)
0.151 (3)
0.065(4)
0.061(4)
0.21 1(3)
0.530(3)
0.709(3)
0.457(3)
0.312(4)
0.197(4)
0.275(3)
0.683(4)
0.61 1(3)
0.556(4)
0.738(4)
0.782(4)
0.730(4)
0.524(3)
0.529(4)
0.399(5)
0.398(4)
0.516(5)
0.447(5)
0.464(5)
0.553(4)
0.690(4)
0.585(4)
0.694(4)
0.471(4)
0.425(4)
0.520(6)

247

Y

0.1784(2)
0.2001(3)
0.1740(4)
-0.0196(3)
0.4538(4)
0.3579(2)
0.3383(4)
0.2203(2)
0.3734(2)
0.495(2)
0.452(2)
0.448(2)
0.447(2)
0.394(2)
0.409(2)
0.550(2)
0.577(3)
0.530(2)
0.538(2)
0.628(3)
0.631(2)
0.617(3)
0.230(3)
0.305(2)
0.272(2)
0.096(2)
0.081(3)
0.240(3)
0.141(3)
0.195(3)
0.120(3)
0.215(3)
0.172(2)
-0.058(3)
-0.035(3)
0.017(2)
0.382(3)
0.476(2)
0.461(4)

Z

0.6681(2)
0.9748(3)
0.5142(3)
0.7241(4)
0.3307(3)
0.6263(2)
0.5976(4)
0.8188(3)
0.8296(3)
0.615(3)
0.555(3)
0.650(3)
0.470(2)
0.475(2)
0.917(2)
0.884(2)
0.779(3)
0.782(3)
0.868(3)
0.989(3)
0.905(3)
0.987(3)
0.841(3)
0.840(3)
0.928(3)
0.904(3)
0.630(3)
1.007(4)
0.976(3)
1.002(3)
0.495(4)
0.462(4)
0.524(3)
0.749(3)
0.670(3)
0.698(3)
0.323(3)
0.282(3)
0.353(4)

B(eq)

2.2(1)
3.4(2)
4.2(2)
3.9(2)
4.4(2)
1.9(1)
3.9(2)
2.6(2)
2.7(2)
2.7(8)
3.1(9)
3.6(9)
1.8(7)
1.5(7)
1.7(7)
1.7(7)
3.6(9)
2.7(8)
1.9(7)
3(1)
2.9(8)
5(1)
4(1)
3.2(8)
4(1)
3.5(9)
3.8(9)
7(1)
3.9(9)
5(1)
6(1)
6(1)
3.1(9)
5(1)
5(1)
3.3(9)
6(1)
32(9)
8(1)

_ Table A.1. continued

248

atom x y 2 WW)
H(31) 0.711(4) 0.318(3) 0.646(3) 4(1)
H(32) 0.655(4) 0.311(3) 0.554(4) 4(1)
H(33) 0.684(5) 0.395(4) 0.595(4) 8(1)

 

249

Table A.2. Atomic positional parameters and equivalent isotropic

displacement parameters (A2) and their estimated standard deviations for

(TMPP)Mo(CO)5 (3).

 

 

atom x y z B(eq)
Mo(l) 0.90870(2) 0.06473(1) 0.23515(2) 246(1)
P(1) 1.08404(6) 0.14210(3) 0.28750(5) 1.93(2)
O(1) 1.1973(2) 0.07929(8) 0.1469(1) 2.59(7)
O(2) 0.9601(2) 0.24137(9) 0.1626(1) 2.98(8)
O(3) 1.1055(2) 0.2138(1) -0.1351(1) 3.55(9)
O(4) 1.2294(2) 0.24812(9) 0.3067(2) 3.05(8)
0(5) 0.9914(2) 0.36540(9) 0.4831(2) 3.38(9)
O(6) 0.9025(2) 0.16813(8) 0.4214(1) 2.77(8)
O(7) 1.3573(2) 0.1573(1) 0.2524(1) 2.81(8)
O(8) 1.5663(2) 0.0678(1) 0.5564(2) 4.8(1)
O( 14) 1.1267(2) 0.08880(9) 0.4772(1) 2.74(8)
O(80) 1.1050(3) -0.0359(1) 0.2643(2) 6.2(1)
O(81) 0.8686(2) 0.0397(1) 0.4577(2) 4.2(1)
O(82) 0.7281(2) 0.1724(1) 0.1971(2) 4.6(1)
O(83) 0.9040(3) 0.0725(1) -0.0002(2) 5.8(1)
O(84) 0.6966(2) -0.0241(1) 0.1690(2) 5.8(1)
C(l) 1.0635(2) 0.2079(1) 0.3582(2) 2.1(1)
C(2) 0.9705(2) 0.2155(1) 0.4116(2) 2.3(1)
C(3) 0.9503(3) 0.2681(1) 0.4523(2) 2.6(1)
C(4) 1.0220(3) 0.3151(1) 0.4425(2) 2.6(1)
C(S) 1.1 176(3) 0.3097(1) 0.3955(2) 2.6(1)
C(6) 1.1363(2) 0.2566(1) 0.3544(2) 2.4(1)
C(7) 1.0964(2) 0.1657(1) 0.1604(2) 2.1(1)
C(8) 1.0321(2) 0.2130(1) 0.1105(2) 2.3(1)
C(9) 1.0371(3) 0.2284(1) 0.0120(2) 2.7(1)
C(10) 1.1049(3) 0.1943(1) -0.0391(2) 2.6(1)
C(11) 1.1627(3) 0.1452(1) 0.0044(2) 2.5(1)
C(12) 1.1547(2) 0.1305(1) 0.1024(2) 2.2(1)
C(13) 1.2381(2) 0.1205(1) 0.3609(2) 2.2(1)
C(14) 1.2390(2) 0.0942(1) 0.4543(2) 2.4(1)
C(15) 1.3447(3) 0.0748(1) 0.5223(2) 2.9(1)
C(16) 1.4551(3) 0.0837(1) 0.4970(2) 3.2(1)
C(17) 1.4600(3) 0.1110(1) 0.4069(2) 3.0(1)
C(18) 1.3541(2) 0.1293(1) 0.3392(2) 2.4(1)
C(22) 0.8899(6) 0.2883(3) 0.1 168(4) 6.0(2)
C(23) 1.2883(4) 0.2966(2) 0.2765(3) 3 .9(1)
C(24) 1.4733(3) 0.1643(2) 0.2284(3) 3.5(1)

Table A.2. continued

250

atom x y z B(eq)
C(25) 1.5693(5) 0.0430(3) 0.6531(3) 5.5(2)
C(26) 1.0598(3) 0.4153(1) 0.4731(3) 3.6(1)
C(27) 0.8068(4) 0.1751(2) 0.4745(3) 3.8(2)
C(28) 1.2705(4) 0.0445(2) 0.0987(3) 4.1(2)
C(31) 1.1526(5) 0.1768(2) -0.1998(3) 4.4(2)
C(32) 1.1212(4) 0.1020(2) 0.5786(2) 3 .6(1)
C(80) 1.0364(3) 0.0001(2) 0.2552(3) 3.7(1)
C(81) 0.8889(3) 0.0507(1) 0.3810(3) 3.2(1)
C(82) 0.7919(3) 0.1339(1) 0.2127(2) 3.1(1)
C(83) 0.9114(3) 0.0709(1) 0.0851(3) 3.6(1)
C(84) 0.7744(3) 0.0086(1) 0.1924(2) 3 .6(1)

 

251

Table A.3. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

(TMPP)Cr(CO)3-01202 (7-CHzC12).

 

 

atom x y z B(eq)
Cr( 1) 0.33850(6) 0.21184(8) 0.13744(6) 1.68(4)
P( 1) 0.2496(1) 0.3509(1) 0.085 84(9) 1.43(7)
O( 1) 0.4215(2) 0.3533(3) 0.1214(2) 1.8(2)
O(2) 0.4750(2) 0.7398(4) 0.0704(2) 2.4(2)
O(3) 0.2068(2) 0.5862(3) 0.0248(2) 2.2(2)
O(4) 0.2673(2) 0.4040(4) -0.0832(2) 2.1(2)
O(5) 0.0214(2) 0.2547(4) -0. 1995(2) 2.7(2)
O(6) 0.0987(2) 0.2313(3) 0.0839(2) 2.0(2)
O(7) 0.3177(2) 0.3206(3) 0.2401(2) 1.9(2)
O(8) 0.1260(2) 0.5244(4) 0.3824(2) 2.4(2)
O(9) 0.0820(2) 0.4772(4) 0.1050(2) 2.2(2)
O(31) 0.4522(3) 0.0401(4) 0.2156(3) 3.6(2)
O(32) 0.21 18(3) 0.0368(4) 0.1477(3) 2.8(2)
O(33) 0.3617(3) 0.0877(4) -0.0118(2) 2.7(2)
C(l) 0.3143(3) 0.4719(5) 0.0716(3) 1.4(3)
C(2) 0.3960(3) 0.4604(5) 0.0952(3) 1.5(3)
C(3) 0.4491(3) 0.5498(5) 0.0940(3) 1.6(3)
C(4) 0.4192(4) 0.6544(5) 0.0679(3) 1.7(3)
C(5) 0.3394(4) 0.6705(5) 0.0429(3) 1 .6(3)
C(6) 0.2875(3) 0.5781(5) 0.0460(3) 1 .5(3)
C(7) 0.1781(3) 0.3281(5) 0.0003(3) 1.3(3)
C(8) 0.1949(3) 0.3547(5) -0.0774(4) 1.8(3)
C(9) 0.1424(3) 0.3290(5) -0. 1427(3) 1.8(3)
C(10) 0.0718(4) 0.2719(5) -0.1315(4) 2.0(3)
C(11) 0.0545(3) 0.2382(5) -0.0569(4) 1.8(3)
C(12) 0.1094(4) 0.2655(5) 0.0079(3) 1.7(3)
C(13) 0.2011(3) 0.4002(5) 0.1714(3) 1.5(3)
C(14) 0.2472(3) 0.3815(5) 0.2442(3) 1.6(3)
C(15) 0.2247(4) 0.4199(5) 0.3162(3) 1.6(3)
C(16) 0.1553(4) 0.4797(5) 0.3161(4) 1.8(3)
C(17) 0.1059(3) 0.4986(5) 0.2458(4) 1.9(3)
C(18) 0.1293(3) 0.4586(5) 0.1751(4) 1.8(3)
C(19) 0.5066(4) 0.3347(6) 0.1321(4) 2.6(3)
C(20) 0.4470(4) 0.8509(6) 0.0507(4) 2.7(3)
C(21) 0.1737(4) 0.6933(6) 0.0031(4) 2.6(3)
C(22) 0.2793(4) 0.4655(7) -0. 1529(4) 3 .9(4)
C(23) -0.0519(4) 0.1979(7) -0. 1918(4) 3 .9(4)

Table A.3. continued

atom

C(24)
C(25)
C(26)
C(27)
C(31)
C(32)
C(33)
Cl(1)
Cl(2)
C(28)
H(l)

H(2)

H(3)

H(4)

H(S)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)

X

0.0366(4)
0.3768(4)
0.1743(4)

-0.0016(4)

0.4097(4)
0.2607(4)
0.3533(3)
0.7246(1)
0.6772(1)
0.6950(5)
0.5045
0.3201
0.1541
0.0067
0.2569
0.0568
0.5171
0.5282
0.5307
0.491 1
0.421 1
0.4102
0.1845
0.1972
0.1 174
0.3331
0.2690
0.2437
-0.0806
-0.0830
-0.041 1
-0.0134
0.0464
0.0353
0.3533
0.4209
0.3949
0.1826
0.2247

252

Y

0.1535(5)
0.3232(6)
0.5084(5)
0.461 1(6)
0.1 1 14(5)
0.1077(6)
0.1386(5)
0.1893(2)
0.3237(2)
0.3250(6)
0.5400
0.7421
0.3501
0.1977
0.4047
0.5386
0.2603
0.3432
0.3882
0.9018
0.8512
0.8740
0.7447
0.7208
0.6863
0.4918
0.4177
0.5284
0.2367
0.1961
0.1226
0.1834
0.0837
0.1412
0.2962
0.2764
0.3987
0.4297
0.5447

Z

0.0964(4)
0.3084(4)
0.4564(4)
0.1077(4)
0.1873(4)
0.1460(3)
0.0451(4)
0.7927(1)
0.6529(1)
0.7569(4)
0.1 106
0.0241

-0. 1944
-0.0499
0.3643
0.2467
0.1517
0.0827
0.1689
0.0539
-0.0017
0.0867
0.0459
-0.0420
-0.0091
-0. 1499
-0. 1978
-0.1577
-0. 1544
-0.2417
-0. 1739
0.0747
0.071 1
0.1516
0.3536
0.2988
0.3176
0.4656
0.4543

B(eq)

2.5(3)
2.9(3)
2.2(3)
2.5(3)
2.0(3)
1.9(3)
1.7(3)
4.0(1)
4.4(1)

Hm
\OQ
A
A
V

PPPP’PPPPPPPPENPP
o—H—mwwr—wao—‘No

4.7

NPWP’PPPP
qqmmmooo

Table A.3. continued

atom

H(30)
H(3 l)
H(32)
H(33)
H(34)
H(35)

X

0.1477
-0.0202
-0.0289
-0.01 17
0.6473
0.7364

253

0.5400
0.5097
0.4782
0.3846
0.3468
0.3778

0.4982
0.1466
0.0573
0.1209
0.7789
0.7723

B(eq)

2.7
3.0
3.0
3.0
4.4
4.4

 

254

Table A.4. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
(TMPP)Cr(CO)4 (8).

 

 

atom x y z B(eq)
Cr( 1) 0.16945(7) 0.80076(5) 0.72908(6) 1.45(4)
P(1) 0.3702(1) 0.81359(8) 0.73413(9) 123(6)
0( 1) 0.5685(3) 0.8343(2) 0.6326(2) 2.0(2)
O(2) 0.3607(3) 0.9617(2) 0.3825(2) 2.6(2)
O(3) 0.1837(3) 0.8865(2) 0.6271(2) 1.5(2)
O(4) 0.6196(3) 0.7909(2) 0.8253(2) 2.0(2)
O(5) 0.6690(3) 1.0310(2) 0.9592(2) 2.2(2)
O(6) 0.3201(3) 0.9637(2) 0.7809(2) 1.6(2)
O(7) 0.4335(3) 0.7050(2) 0.5863(2) 2.1(2)
O(8) 0.5959(3) 0.5138(2) 0.7901(2) 2.1(2)
O(9) 0.4172(3) 0.7297(2) 0.8891(2) 1.6(2)
O(41) -0.0802(3) 0.7783(3) 0.7018(3) 3.6(2)
O(42) 0.1652(3) 0.6807(2) 0.5869(3) 2.8(2)
O(43) 0.1709(3) 0.6779(2) 0.8634(3) 3.0(2)
O(44) 0.1248(3) 0.9040(2) 0.8795(3) 3.0(2)
C(l) 0.3774(4) 0.8562(3) 0.6271(3) 1.1(2)
C(2) 0.4737(4) 0.8624(3) 0.5852(4) 1 .7(2)
C(3) 0.4715(4) 0.8955(3) 0.5026(3) 1.8(2)
C(4) 0.3730(5) 0.9273(3) 0.4628(4) 1.9(3)
C(5) 0.2763(4) 0.9265(3) 0.5038(3) 1.6(2)
C(6) 0.2806(4) 0.8903(3) 0.5839(3) 1.2(2)
C(7) 0.4657(4) 0.8755(3) 0.8059(3) 1.1(2)
C(8) 0.5774(4) 0.8594(3) 0.8434(3) 1.5(2)
C(9) 0.641 1(4) 0.9120(3) 0.8956(3) 1.7(2)
C(10) 0.5970(4) 0.9829(3) 0.9100(3) 1.5(2)
C(11) 0.4878(4) 1.0011(3) 0.8739(3) 1.4(2)
C(12) 0.4258(4) 0.9476(3) 0.8224(3) 1.3(2)
C(13) 0.4333(4) 0.7203(3) 0.7388(3) 1.3(2)
C(14) 0.4640(4) 0.6770(3) 0.6695(3) 1 .6(2)
C(15) 0.5192(4) 0.6081(3) 0.6832(3) 1.6(2)
C(16) 0.5424(4) 0.5801(3) 0.7689(4) 1.7(2)
C(17) 0.5057(4) 0.6188(3) 0.8394(3) 1.5(2)
C(18) 0.4521(4) 0.6864(3) 0.8229(3) 1.4(2)
C(19) 0.6715(4) 0.8369(3) 0.5955(4) 2.8(3)
C(20) 0.4522(5) 0.9581(4) 0.3317(4) 2.8(3)
C(21) 0.1055(4) 0.9467(3) 0.6105(4) 2.0(3)

C(22)

0.7288(5)

0.7700(3)

0.8650(4)

2.3(3)

Table A.4. continued

atom

C(23)
C(24)
C(25)
C(26)
C(27)
C(41)
C(42)
C(43)
C(44)
H( 1)

H(2)

H(3)

H(4)

H(S)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H( 12)
H(13)
H(14)
H(15)
H( 16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)

X

0.6331(5)
0.2709(5)
0.4841(5)
0.6533(5)
0.4320(5)
0.0161(5)
0.1733(5)
0.1731(5)
0.1469(4)
0.5370
0.2093
0.7151
0.4566
0.5406
0.5176
0.7300
0.6636
0.6895
0.4673
0.4332
0.5170
0.1414
0.0787
0.0442
0.6904
0.6188
0.5664
0.3168
0.1982
0.2650
0.4656
0.4571
0.5634
0.6865
0.6014
0.7103
0.4058
0.3908
0.5095

255

Y

1 .1075 (3)
1.0338(3)
0.6732(4)
0.4787(3)
0.7003(3)
0.7900(3)
0.7277(3)
0.7262(3)
0.8691(3)
0.8963
0.9502
0.8996
1.0489
0.5806
0.5986
0.8155
0.8092
0.8878
0.9070
0.9849
0.9801
0.9929
0.9487
0.9386
1.1353
1.1292
1.1087
1.0741
1.0380
1.0361
0.6213
0.6986
0.6787
0.4330
0.4684
0.51 16
0.7358
0.6547
0.6906

Z

0.9663(4)
0.8008(4)
0.5152(4)
0.7248(4)
0.9762(3)
0.7097(3)
0.6400(4)
0.81 13(4)
0.8207(4)
0.4739
0.4773
0.9216
0.8844
0.6348
0.8976
0.6359
0.5417
0.5841
0.3191
0.2779
0.3643
0.6285
0.5491
0.6428
1.0012
0.9090
0.9935
0.7855
0.7680
0.8622
0.5095
0.4617
0.5269
0.7477
0.6736
0.7096
1 .0153
0.9776
0.9942

B(eq)

2.7(3)
2.3(3)
3.2(3)
2.8(3)
2.3(2)
2.3(3)
1.8(3)
2.0(3)
1.9(3)

.N
N

PPPPPWPPPPPPPPPNF’PPP’PP’PPfffP?‘
\Jquwwoooooooooooomwu-phkhA-hwwwooxoqoo

Table A.4. continued

atom
H(3 1)

H(32)
H(33)

X

0.7458
0.7822
0.7315

256

y 2
0.7208 0.8460
0.8048 0.8481
0.7704 0.9275

B(eq)

 

257

Table A.5. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[Ni(TMPP-0)2][BF4]-2(CH3)2C0 (1 5-2(CH3)2C0).

 

 

atom x y 2 Wm)
Ni( 1) 0.3762(1) 0.13449(8) 0.85516(6) 153(8)
P( 1) 0.4031(2) 0.0866(2) 0.7485(1) 1.6(2)

P(2) 0.3626(2) 0.2968(2) 0.8108(1) 1.6(2)
0(1) 0.1975(5) 0.1538(5) 0.8418(3) 2.6(5)
0(2) -0.0728(5) 0.1472(5) 0.6810(3) 2.9(5)
0(3) 0.3246(5) 0.0381(4) 0.6259(3) 2.4(5)
0(4) 0.3903(5) -0.0044(4) 0.9024(3) 2.0(4)
0(5) 0.5653(5) -0.3474(4) 0.9013(3) 2.2(4)
0(6) 0.5496(4) -0.0886(4) 0.6744(3) 2.0(4)
0(7) 0.3148(4) 0.2436(4) 0.6041(3) 2.0(4)
0(8) 0.6812(5) 0.2154(4) 0.4733(3) 2.7(5)
0(9) 0.6476(5) 0.0430(4) 0.7301(3) 2.1(4)
0(10) 0.5525(5) 0.1212(5) 0.8717(3) 2.4(5)
0(11) 0.8010(5) 0.2876(5) 0.9108(4) 3 .4(5)
O(12) 0.4440(5) 0.4701(4) 0.7918(3) 2.7(5)
O(13) 0.1965(5) 0.5106(4) 0.8215(3) 2.9(5)
0(14) 0.1251(5) 0.4068(5) 1.0867(3) 3 .2(5)
0(15) 0.3373(4) 0.1680(4) 0.9505(3) 1.8(4)
0(16) 0.5123(5) 0.3582(4) 0.6727(3) 2.3(4)
O(17) 0.2180(5) 0.5709(5) 0.5107(3) 3.4(5)
0( 18) 0.1367(5) 0.3705(4) 0.7578(3) 2.3(5)
C(l) 0.2596(7) 0.1033(6) 0.7295(4) 1.9(7)
C(2) 0.1692(7) 0.1386(6) 0.7787(4) 1 .8(6)
C(3) 0.0572(7) 0.1544(6) 0.7646(5) 2.2(7)
C(4) 0.0334(7) 0.1333(6) 0.7007(5) 2.1(7)
C(5) 0.1219(7) 0.0927(6) 0.6521(5) 2.2(7)
C(6) 0.2315(7) 0.0801(6) 0.6669(5) 1 .7(6)
C(7) 0.4655(6) -0.0456(6) 0.7862(4) 1 .5(6)
C(8) 0.4419(7) -0.0740(6) 0.8646(4) 1 .6(6)
C(9) 0.4717(7) -0. 1754(6) 0.9048(4) 1 .6(6)
C(10) 0.5276(7) —0.2468(6) 0.8671(4) 1 .5(6)
C(11) 0.5547(6) -0.2219(6) 0.7888(4) 1.6(6)
C(12) 0.5241(7) -0. 1222(6) 0.7496(4) 1 .7(6)
C(13) 0.4809(7) 0.1370(6) 0.6657(4) 1 .3(6)
C(14) 0.4292(7) 0.2058(6) 0.5998(4) 1 .7(7)
C(15) 0.4924(8) 0.2330(6) 0.5334(4) 2.1(7)
C(16) 0.6093(7) 0.1935(6) 0.5342(5) 2.1(7)

Table A.5. continued

atom

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)
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)
H(1)

H(2)

H(3)

X

0.6634(7)
0.6003(7)
0.5001(7)
0.5799(7)
0.6799(7)
0.7003(7)
0.6262(7)
0.5251(7)
0.2704(7)
0.2067(7)
0.1598(7)
0.1745(7)
0.2336(7)
0.2824(6)
0.3223(6)
0.3988(7)
0.3624(7)
0.2457(8)
0.1669(7)
0.2072(7)
0.1 167(8)

-0. 1664(8)

0.3090(8)
0.5377(7)
0.6168(8)
0.2538(8)
0.6319(8)
0.7562(8)
0.6265(8)
0.8158(8)
0.4619(8)
0.1578(8)
0.1479(7)
0.5929(7)
0.1030(8)
0.0185(8)
-0.0027
0.1060
0.4533

258

Y

0. 1287(6)
0.1025(6)
0.2974(7)
0.2061(6)
0.2047(6)
0.2950(7)
0.3858(6)
0.3848(7)
0.3398(6)
0.4384(6)
0.4586(6)
0.3792(7)
0.2824(6)
0.2607(6)
0.3719(6)
0.3995(6)
0.4675(6)
0.5046(6)
0.4739(6)
0.4076(6)
0.1587(8)
0.1877(7)
-0.0078(7)
-0.3788(6)
-0. 1631(7)
0.2895(7)
0.2852(7)
-0.0279(7)
0.0243(6)
0.3801(8)
0.5648(6)
0.6128(7)
0.3337(7)
0.3949(7)
0.6034(8)
0.4125(9)
0.1794
0.0746
-0.1943

Z

0.5981(5)
0.6629(4)
0.8312(4)
0.8657(4)
0.8937(5)
0.8834(4)
0.8489(5)
0.8242(4)
0.8853(4)
0.8894(5)
0.9558(5)
1.0218(5)
1.0210(4)
0.9524(4)
0.7179(4)
0.6597(5)
0.5907(5)
0.5802(4)
0.6347(4)
0.7020(4)
0.9036(5)
0.7287(5)
0.5702(5)
0.9807(5)
0.6355(5)
0.5355(5)
0.4053(5)
0.7259(5)
0.9145(5)
0.9171(6)
0.7820(5)
0.8253(6)
1.1566(5)
0.6195(5)
0.4891(5)
0.7499(6)
0.7982

0.6102

0.9576

B(eq)

2.1(7)
1.8(7)
1.9(7)
1.8(6)
2.1(7)
2.0(7)
2.2(7)
2.1(7)
1.8(6)
2.1(7)
2.2(7)
2.3(7)
1.9(7)
1.6(6)
1.4(6)
2.1(7)
2.0(7)
2.1(7)
1.8(6)
1.7(6)
4(1)
3.1(8)
3.2(8)
2.4(7)
3.3(8)
2.7(7)
3.4(8)
3.3(8)
2.8(7)
4(1)
3.0(8)
3.8(8)
3.2(8)
2.8(7)
4.1(9)
5(1)
2.6
2.6
1.9

Table A.5. continued

atom

H(4)

H(5)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(13)
H( 14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
H(31)
H(32)
H(33)
H(34)
H(35)
H(36)
H(37)
H(38)
H(39)
H(40)
H(41)
H(42)

X

0.5933
0.4562
0.7439
0.7318
0.6430
0.1 178
0.2418
0.4152
0.0880
0.1477
0.0500
0.0980

-0.1667
-0.2356
-0. 1589

0.2812
0.2558
0.3796
0.4574
0.5693
0.5680
0.5777
0.6290
0.6880
0.2803
0.2659
0.1749
0.5891
0.6905
0.5833
0.7799
0.7519
0.8093
0.5965
0.7007
0.6301
0.8892
0.8080
0.7597

259

Y

-0.27 28
0.2774
0.1024
0.1433
0.4470
0.5253
0.2302
0.4879
0.4979
0.1694
0.2127
0.0974
0.2528
0.1920
0.1450
-0.0632
0.0401
-0.0306
-0.361 1
-0.4496
-0.3466
-0.2106
-0.1312
-0. 1967
0.3437
0.2410
0.3140
0.3474
0.2953
0.2589
-0.0641
-0.07 33
0.0063
-0.0282
0.01 19
0.0268
0.3664
0.4274
0.4071

Z

0.7636
0.4889
0.5971
0.9190
0.8421
0.9577
1.0666
0.5522
0.6259
0.9436
0.8879
0.9207
0.7293
0.7097
0.7786
0.5946
0.5351
0.5442
0.9891
0.9982
1.0074
0.6390
0.5838
0.6582
0.5059
0.5077
0.5478
0.4157
0.3681
0.3871
0.7756
0.6991
0.7002
0.9150
0.8909
0.9649
0.9344
0.8689
0.9520

wwwwwseewwweeewwwwwwwww
##OOCHHHNNNOOOOOOOOOOOWOO

:“PPP‘. .
qq<¢

Table A.5. continued

atom

H(43)
H(44)
H(45)
H(46)
H(47)
H(48)
H (49)
H(SO)
H(S 1)
H(52)
H(53)
H(54)
H(55)
H(56)
H(57)
H (5 8)
H(59)
H(60)
F( 1 )

F(2)

F (3)

F (4)

B( 1 )

0(1 9)
C(53)
C(54)
C(55)
H(61 )
H(62)
H(63)
H(64)
H(65)
H(66)
0(20)
C(57)
C(58)
H(67)
H (68)
H(69)

X

0.4744
0.5264
0.3969
0.2098
0.1528
0.0850
0.1083
0.1236
0.2272
0.6675
0.5853
0.5795
0.0549
0.0967
0.0809
-0.0026
-0.0013
-0.0203
0.3410(4)
0.1532(5)
0.2451(5)
0.2098(5)
0.2367(9)
0.103(1)
0.030(1)
0.020(1)
-0.045(2)
0.0880
-0.0426
0.0099
—0.08 12
-0. 1002
-0.0002
0.971(1)
0.793(2)
0.936(2)
0.7604
0.7501
0.7934

260

Y

0.5716
0.5690
0.6172
0.6247
0.6560
0.6258
0.3622
0.2782
0.31 15
0.3581
0.3870
0.4641
0.6370
0.6483
0.5469
0.4823
0.4028
0.3805
0.3997(4)
0.4159(5)
0.4214(4)
0.5493(4)
0.4465(8)
0.1250(9)
0.160(1)
0.253(1)
0.097(1)
0.2462
0.2672
0.3060
0.0851
0.1317
0.0353
0.1451(8)
0.148(1)
0.1 13(2)
0.2127
0.1391
0.0982

Z

0.8296
0.7487
0.761 1
0.8522
0.7756
0.8508
1.1965
1.1565
1.1640
0.6358
0.5713
0.6160
0.5242
0.4400
0.4889
0.7464
0.7053
0.7926
0.3695(3)
0.3813(3)
0.2682(3)
0.3196(3)
0.3348(6)
0.4534(6)
0.4080(8)
0.3499(8)
0.41 1(1)
0.3183
0.3203
0.3728
0.4599
0.3742
0.401 1
0.1975(6)
0.190(1)
0.089(2)
0.1979
0.1547
0.2361

Table A.5. contim‘red

atom x
H(70) 0.9228
H(71) 1.0136

H(72) 0.8890

261

Y

0.051 1
0.1077
0.1647

0.0931
0.0740
0.0518

B(eq)

25.7
25.7
25.7

262

Table A.6. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
[Pd(TMPP)2][BF4]2 (1 6).

 

 

atom x y z B(eq)
Pd(l) 0.24134(3) 0.24438(3) 0.2662 1.91 (3)
P( 1) 0.2393(1) 0.3218(2) 0.1573(2) 1.7(1)
P(2) 0.2520(1) 0.3162(2) 0.3789(3) 2.0(1)
0(1) 0.2143(4) 0.1686(4) 0.1634(5) 3 .0(4)
0(2) 0.0293(4) 0.1543(4) -0.0230(5) 4.2(4)
0(3) 0.1236(3) 0.3860(4) 0.0446(5) 2.8(4)
0(4) 0.3583(3) 0.2257(4) 0.1984(5) 2.5(3)
0(5) 0.4361(3) 0.2006(4) -0.0771(5) 2.7(4)
0(6) 0.2573(3) 0.3653(5) -0.0138(6) 2.5(4)
0(7) 0.3269(3) 0.4564(4) 0.1 121(5) 2.4(3)
0(8) 0.1690(3) 0.6426(4) 0.1925(5) 2.9(4)
0(9) 0.1317(3) 0.3838(4) 0.2348(5) 2.4(4)
0(10) 0.2622(4) 0.1622(4) 0.3637(5) 2.7(3)
0(1 1) 0.4372(4) 0.1071(4) 0.5400(5) 3.3(4)
O(12) 0.3739(3) 0.3640(4) 0.4879(5) 2.5(4)
O(13) 0.1281(3) 0.2293(4) 0.3394(5) 2.8(4)
0(14) 0.0584(3) 0.1968(4) 0.6181(5) 3.1(4)
0(15) 0.2392(4) 0.3554(5) 0.5538(6) 2.4(4)
O(16) 0.1672(4) 0.4500(4) 0.4302(5) 2.8(4)
0(17) 0.3278(4) 0.6359(4) 0.3544(5) 2.9(4)
0(18) 0.3615(3) 0.3781(4) 0.3027(5) 2.4(3)
C(l) 0.1716(5) 0.2760(5) 0.1014(7) 1.9(2)
C(2) 0.1696(5) 0.1986(5) 0.1090(7) 2.1(2)
C(3) 0.1219(5) 0.1546(6) 0.0714(7) 2.8(2)
C(4) 0.0787(5) 0.1902(6) 0.0208(7) 3 .0(2)
C(5) 0.0783(5) 0.2655(6) 0.0109(7) 3 .0(2)
C(6) 0.1228(5) 0.3112(6) 0.0507(7) 2.3(2)
C(7) 0.3069(5) 0.2954(6) 0.0909(7) 1 .9(2)
C(8) 0.3552(5) 0.2456(6) 0.1 150(6) 2.0(2)
C(9) 0.3990(5) 0.2145(6) 0.0584(8) 2.3(2)
C(10) 0.3937(5) 0.2374(6) -0.0264(7) 2.0(2)
C(l 1) 0.3504(5) 0.2900(5) -0.0528(7) 2.0(2)
C(12) 0.3065(4) 0.3174(6) 0.0058(7) 2.0(2)
C(13) 0.2246(5) 0.4218(5) 0.1676(7) 1.6(2)
C(14) 0.2680(5) 0.4775(6) 0.1403(7) 2.2(2)
C(15) 0.2499(5) 0.5538(7) 0.1491(8) 2.5(3)
C( 16) 0.1905(5) 0.5713(6) 0.1817(7) 2.2(2)

Table A.6. continued

atom

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)
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)
F ( 1)

X

0.1487(5)
0.1664(5)
0.3174(5)
0.3 108(4)
0.3518(5)
0.4003(5)
0.4102(5)
0.3687(5)
0.1854(5)
0.1339(5)
0.0927(5)
0.0993(5)
0.1470(5)
0.1890(4)
0.2682(5)
0.2271(5)
0.2460(4)
0.3044(5)
0.3460(5)
0.3268(5)
0.2415(6)
0.0278(6)
0.0730(6)
0.4096(5)
0.4380(6)
0.4856(6)
0.3688(5)
0.2102(5)
0.0681(4)
0.2380(6)
0.2545(6)
0.4153(5)
0.0743(5)
0.0688(6)
0.2403(6)
0.1253(6)
0.2864(5)
0.4244(4)
0.6061(4)

263

Y

0.5177(6)
0.4424(5)
0.2627(6)
0.1842(6)
0.1345(5)
0.1604(6)
0.2369(6)
0.2883(5)
0.291 1(6)
0.2444(6)
0.2136(6)
0.2302(6)
0.2791(6)
0.3096(6)
0.4150(6)
0.4735(6)
0.5484(6)
0.5666(6)
0.5105(6)
0.4373(5)
0.0975(9)
0.0778(6)
0.4233(6)
0.1795(7)
0.2198(8)
0.1272(7)
0.5089(7)
0.7012(6)
0.3995(6)
0.0886(6)
0.3938(9)
0.3916(6)
0.1869(7)
0.2021(8)
0.3923(9)
0.5063(7)
0.6949(6)
0.3944(5)
0.1 1 18(4)

2

0.2105(7)
0.2038(7)
0.4273(6)
0.4174(6)
0.4549(6)
0.5046(7)
0.5154(7)
0.4772(7)
0.4480(7)
0.4237(7)
0.4826(8)
0.5649(7)
0.5918(7)
0.5330(7)
0.3730(7)
0.4010(7)
0.3989(8)
0.3631(7)
0.3312(7)
0.3351(7)
0.139(1)

-0.0181(8)

-0.001(1)
0.2249(8)

-0. 1628(9)

0.5987(8)
0.0786(9)
0.1646(9)
0.264(1)

0.3703(8)
-0.095( 1)
0.5514(8)
0.3105(8)
0.7071(9)
0.6351(9)
0.4676(9)
0.383(1)

0.272(1)

0.7613(8)

B(CQ)

2.1(2)
2.0(2)
2.3(2)
1.9(2)
1.9(2)
2.5(2)
2.3(2)
1.9(2)
1.9(2)
2.2(2)
2.5(2)
2.2(2)
2.2(2)
1.8(2)
2.1(2)
2.0(2)
1.5(2)
2.2(2)
2.0(2)
1.9(2)
4.3(8)
4.0(6)
4.4(7)
3.8(6)
4.7(7)
4.2(6)
3.5(6)
3.3(6)
3.2(5)
2.6(5)
3.3(7)
3.4(6)
3.2(6)
4.2(7)
2.4(6)
3.6(6)
3.4(6)
3.0(5)
7.4(5)

Table A.6. continued

atom

P(2)
F(3)
F(4)
B( 1)
F(S)
F(6)
W)
W)
8(2)
H(1)
H(2)
H(3)
H(4)
H(S)
H(6)
H(7)
H(8)
H(9)
H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(l9)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
11(30)

X

0.5938(4)
0.6370(6)
0.5354(5)
0.5923(6)
0.8870(4)
0.9070(5)
0.9755(4)
0.8879(7)
0.9129(7)
0.1 196
0.0465
0.4309
0.3503
0.2788
0.1085
0.3464
0.4453
0.0594
0.1509
0.2189
0.3866
0.2079
0.2645
0.2703
0.0244
-0.0085
0.0662
0.0806
0.0722
0.0326
0.4060
0.4078
0.4495
0.4499
0.4688
0.3966
0.5076
0.5155
0.4663

264

Y

0.0097(5)
0.0022(6)
0.0266(8)
0.0371(8)
0.1017(5)
0.0037(5)
0.0425(6)

-0.0122(6)

0.0326(8)
0.1021
0.2876
0.1796
0.3073
0.5925
0.5316
0.0821
0.2542
0.1804
0.2916
0.5863
0.5234
0.0620
0.1032
0.0806
0.0630
0.0595
0.0578
0.4758
0.4055
0.4132
0.1706
0.1332
0.2037
0.2710
0.1893
0.2122
0.0833
0.1603
0.1512

Z

0.6803(6)
0.8079(8)
0.7945(7)
0.764(1 )
0.7639(9)
0.8494(5)
0.752(1)
0.7159(7)
0.772(1)
0.0809
-0.0244
0.0760
-0. 1093
0.1326
0.2347
0.4463
0.5488
0.4650
0.6497
0.4217
0.3075
0.1318
0.0877
0.1816
0.0391
-0.0484
0.0416
-0.0010
-0.0573
0.0251
0.2836
0.1956
0.2134
-0. 1684
-0.1908
-0. 1870
0.6169
0.5727
0.6455

MMMMMMPPPMMMPPPMS‘P‘P!‘
OOOQQQO‘aab-DWWOOMOONNNMOO

Table A.6. continued

atom

H(3 1)
H(32)
H(33)
H(34)
H(35)
H(36)
H(37)
H(3 8)
H(39)
H(40)
H(41)
H(42)
H(43)
H(44)
H (45)
H(46)
H(47)
H(48)
H(49)
H(50)
H(5 1)
H(52)
H(53)
H (54)
H(55)
H(56)
H(57)
H(58)
H(59)
H(60)
H(61)
H(62)
H(63)
H(64)
H(65)
H(66)

X

0.4077
0.3494
0.3782
0.2499
0.2179
0.1900
0.0704
0.0432
0.0484
0.2192
0.2063
0.2723
0.2930
0.2501
0.2185
0.4015
0.4582
0.4141
0.0355
0.0772
0.0744
0.0362
0.1099
0.0672
0.2407
0.2780
0.2031
0.1463
0.1 159
0.0862
0.3074
0.2474
0.2769
0.4434
0.4214
0.4504

265

0.4848
0.5320
0.5459
0.6990
0.6959
0.7483
0.4339
0.4206
0.3543
0.0817
0.0806
0.0539
0.4207
0.3536
0.4264
0.3733
0.3752
0.4448
0.2125
0.1807
0.1391
0.1748
0.1819
0.2533
0.3556
0.4225
0.4230
0.5284
0.5440
0.4834
0.7417
0.6941
0.6878
0.3498
0.4306
0.4135

0.0619
0.0312
0.1 198
0.1942
0.1061
0.1749
0.3099
0.2202
0.2830
0.4242
0.3282
0.3630
-0.1071
-0. 1341

-0.1002

0.6045
0.5409
0.5516
0.3240
0.2513
0.3369
0.7358
0.7207
0.7238
0.6784
0.6394
0.6409
0.5145
0.4271
0.4855
0.3753
0.3514
0.4407
0.2500
0.2279
0.3158

PPPPPPPP§PPPMMMPS~PPPP¥PPPPPPPP
ONChOH-dwawwooewwwcoct—F‘HOOOHr-H—oooooo

 

266

Table A.7. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[Pt(NCCH3)2(TMPP)2][BF4]2 (18).

 

 

atom x y z B(eq)
Pt( 1) 0.24248(2) -0.24945(2) 0.24773(3) 1.75(1)
P(l) 0.3513(1) -0.3168(1) 0.1661(2) 1.99(7)
P(2) 0.1291(1) ~0. 1786(1) 0.3173(2) 206(7)
0(1) 0.5720(3) -0.3539(3) 0.2666(4) 3.3(2)
0(2) 0.5079(4) -0.5673(3) 0.3777(5) 4.1(2)
0(3) 0.2478(3) -0.4376(3) 0.1717(4) 2.6(2)
0(4) 0.1397(3) -0.3447(3) 0.0115(4) 2.8(2)
0(5) 0.2144(4) -0.4631(3) -0.3194(4) 3.9(2)
0(6) 0.4630(3) -0.3869(3) 0.0298(4) 3 .0(2)
0(7) 0.4895(4) -0.2346(3) 0.3732(4) 3 .5(2)
0(8) 0.6553(4) -0.0731(4) 0.2498(5) 4.9(3)
0(9) 0.3780(4) -0.2363(3) -0.0021(4) 3.7(2)
0(10) -0.0140(4) -0.0710(3) 0.3506(5) 3.7(2)
0(11) 0.1228(4) 0.1431(3) 0.3001(6) 4.9(3)
O(12) 0.3031(3) -0.0781(3) 0.3409(5) 3.5(2)
O(13) 0.0424(3) -0.3262(3) 0.2799(4) 3.1(2)
0(14) -0.2534(4) -0.3219(3) -0.0086(5) 4.1(2)
0(15) -0.0026(4) -0. 1207(3) 0.1201(5) 3.9(2)
O(16) 0.2892(3) -0. 1453(3) 0.5092(4) 3.1(2)
0(17) 0.1635(4) -0.2019(4) 0.7710(5) 5 .4(3)
0(18) -0.0425(3) -0.2141(3) 0.3981(4) 3.3(2)
N(l) 0.2223(4) -0. 1877(4) 0.1402(5) 2.9(3)
N(2) 0.2667(4) -0.3061(3) 0.3610(5) 2.3(2)
C(l) 0.4078(5) -0.3924(4) 0.2282(6) 1.9(2)
C(2) 0.5070(5) -0.4028(4) 0.2749(6) 2.3(3)
C(3) 0.5384(5) -0.4612(4) 0.3237(6) 2.6(3)
C(4) 0.4698(5) -0.51 19(4) 0.3250(6) 2.9(3)
C(5) 0.3713(5) -0.5070(4) 0.2742(6) 2.7(3)
C(6) 0.3429(5) -0.4470(4) 0.2262(6) 2.2(3)
C(7) 0.3020(5) -0.3647(4) 0.0202(6) 2.3(3)
C(8) 0.2032(5) -0.3732(4) -0.0431(6) 2.2(3)
C(9) 0.1704(5) -0.4068(4) -0. 1569(6) 2.7(3)
C(10) 0.2378(5) -0.4319(4) -0.2087(6) 3.0(3)
C(l 1) 0.3373(5) -0.4273(4) -0. 1468(6) 3.0(3)
C(12) 0.3679(5) -0.3942(4) -0.0357(6) 2.5(3)
C(13) 0.4400(5) -O.2435(4) 0.1839(6) 2.4(3)
C(14) 0.5064(5) -0.2096(4) 0.2906(7) 2.9(3)

Table A.7. continued

atom

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)
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)

X

0.5795(5)
0.5852(5)
0.5198(5)
0.4481(5)
0.1396(5)
0.0595(5)
0.0567(6)
0.1362(6)
0.2196(5)
0.2215(5)
0.0156(5)
-0.0205 (5)
-0. 1099(5)
-0. 1656(5)
-0.1331 (5)
-0.0418(5)
0.1266(5)
0.2159(5)
0.2265(5)
0.1446(6)
0.0558(5)
0.0458(5)
0.6734(5)
0.4428(7)
0.1759(6)
0.0381(5)
0.1 150(6)
0.5350(5)
0.5640(7)
0.6567(7)
0.3957(7)
-0.0999(6)
0.1980(7)
0.391 1(6)
0.0053(7)
-0.3124(6)
-0.0603(7)
0.3827(6)
0.0839(8)

267

Y

-0. 1559(5)
-0. 1294(5)
-0. 1562(5)
-0.21 17(4)
-0.0779(4)
-0.0343 (4)
0.0395(4)

0.0721(4)

0.0351(4)

-0.0387(4)
-0.2185(4)
-0.2907(4)
-0.3240(4)
-0.2868(5)
-0.2186(5)
-0. 1860(4)
-0. 1855(4)
-0. 1681(4)
-0. 1736(5)
-0.1967(5)
-0.21 15(4)
-0.2049(4)
-0.3674(5)
-0.6156(6)
-0.4933(5)
-0.3605(5)
-0.4668(5)
-0.4093(5)
-0.2169(5)
-0.0386(6)
-0.2249(6)
-0.0314(5)
0.1799(5)

-0.0383(6)
-0.3901(5)
-0.2845(6)
-0.0786(6)
-0. 1238(7)
-0.2314(6)

Z

0.3097(7)
0.2214(7)
0.1 160(7)
0.0991(7)
0.3313(6)
0.3374(7)
0.3293(8)
0.3159(7)
0.3206(7)
0.331 1 (6)
0.21 13(6)
0.2069(7)
0.1344(7)
0.0593(6)
0.0515(7)
0.1265(7)
0.4513(6)
0.5392(7)
0.6448(7)
0.6636(7)
0.5825(7)
0.4790(6)
0.3016(9)
0.3957(8)
0.1537(8)
-0.0452(7)
-0.3875 (6)
-0.0205(7)
0.4789(7)
0.1601(9)
—0.0988(7)
0.352(1)
0.2826(8)
0.355(1)
0.3001(9)
-0.0906(8)
0.047(1)
0.5925(9)
0.7937(9)

B(eq)

3.6(3)
3.5(3)
3.5(3)
3.1(3)
2.3(3)
2.9(3)
3.8(3)
3.3(3)
3.1(3)
2.8(3)
2.2(3)
2.8(3)
3.2(3)
3.3(3)
3.3(3)
3.1(3)
2.3(3)
2.9(3)
3.6(3)
3.8(3)
3.0(3)
2.6(3)
5.0(4)
5.3(4)
4.5(4)
3.8(3)
3.8(3)
4.0(3)
4.9(4)
5.9(5)
4.8(4)
5.6(4)
4.8(4)
6.9(5)
5.1(4)
5.4(4)
6.3(5)
6.3(5)
6.1(5)

Table A.7. continued

atom

C(54)
C(71)
C(72)
C(81)
C(82)
F(l)
P(2)
F(3)
F(4)
B(l)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)

X

-0. 1273(6)

0.2191(7)
0.219(1)
0.2724(5)
0.2775(6)
0.1772(4)
0.2294(4)
0.0868(5)
0.1 132(7)
0.1510(7)
0.6059
0.3248
0.1028
0.3832
0.6252
0.5233
0.0017
0.2747
-0. 1322
-0.1712
0.2875
0.0010
0.6835
0.7091
0.6950
0.4077
0.3984
0.4789
0.1 139
0.1886
0.1765
0.0032
0.0195
0.0239
0.0927
0.1091
0.0768
0.5237
0.5318

268

Y

-0.2231(6)
-0. 1471(5)
-0.0891(7)
-0.3382(5)
-0.3785(6)
0.3585(3)
0.4314(5)
0.4471(4)
0.3475(4)
0.3940(6)
-0.4669
—0.5432
-0.4122
-0.4472
-0.1374
-0.1374
0.0678
0.0592
-0.3717
-0.1944
-0. 1620
-0.2263
-0.4150
-0.3286
-0.3676
-0.5860
-0.6425
-0.6504
-0.4780
-0.5396
-0.5001
-0.3367
-0.3419
-0.4137
-0.4171
-0.4899
-0.4957
-0.4615
-0.3805

Z

0.4266(8)
0.0888(8)
0.027(1)
0.4264(7)
0.5090(8)
0.2662(4)
0.4358(6)
0.3324(6)
0.3958(8)
0.3575(9)
0.3560
0.2723
-0.1980
-0. 1820
0.3819
0.0564
0.3327
0.3167
0.1367
-0.0029
0.7026
0.5981
0.2588
0.2917
0.3776
0.4388
0.3265
0.4339
0.1 160
0.1 101
0.2228
0.0020
-0. 1096
-0.0660
-0.3819
—0.4622
-0.3637
-0.0579
-0.07 21

PPPWPPPPPPP
vocqmwmmNN

9999
#OOO

9‘
A

PPPPPPMMMQ
aoamamaabA

PP
mm

Table A.7. continued

atom

mw)
mu)
mm)
my)
my)
m%)
m%)
mm)
mm)
mm)
mm)
mu)
mm)
mm)
mM)
m“)
m%)
mu)
mm)
mm)
mm)
mm)
H(52)
my)
my)
H(55)
mm)
H(57)
mm)
H(59)
mm)
H(61)
mm)
mm)
ma)
mm)
mm)
ma)
mm)

X

0.5975
0.5449
0.6227
0.5741
0.7080
0.6665
0.5964
0.4524
0.3415
0.4049
-0.0834
-0.1280
-0. 1454
0.2556
0.2100
0.1791
0.4417
0.3820
0.4082
-0.0464
-0.0182
0.0556
-0.3257
-0.2784
-0.3720
-0.0231
-0.0801
-0.1 161
0.4062
0.4269
0.3772
0.0307
0.0645
0.1041
-0. 1323
-0. 1834
-0. 1224
0.2799
0.2076

269

-0.4010
-0.2375
-0.2378
-0. 1635
-0.0005
-0.0765
-0.0169
-0.2494
-0.2454
-0.1722
0.0127

-0.0175
-0.0633
0.1854

0.1508

0.2285

-0.0724
-0.0166
0.0005

-0.3759
-0.4285
-0.4087
-0.2357
-0.2799
-0.3136
-0.0351
-0.1091
-0.0634
-0. 1651
-0.1 100
-0.0820
-0. 1999
-0.2812
-0.2325
-0. 1793
-0.2300
-0.2660
-0.0612
-0.1133

0.0347
0.5286
0.4719
0.5066
0.1879
0.1014
0.1334
-0.1058
-0.1629
-0.0909
0.41 19
0.2843
0.3612
0.3450
0.2185
0.2726
0.3583
0.2947
0.4221
0.3284
0.2329
0.3525
-0.0544
-0. 1389
-0.1320
0.0528
-0.0265
0.0674
0.6234
0.5602
0.6490
0.77 89
0.7481
0.8693
0.4805
0.3623
0.4559
0.0579
-0.0484

1“ cu
ooh)
1.0
v

QWWWMMMQQP‘MMV‘NNNMV‘M
Nwwwoooooooaoooooooup—uxoxoo

99999
MMMNN

NNSNSN
oaamom

>‘>‘.“
won»

999
O\O\O\

\D
.p.

9.4

Table A.7. continued

atom

H(69)
H(70)
H(71)
H(72)
F(S)
F (6)
F(7)
F (8)
B(2)

X

0.1687
0.2147
0.3212
0.3000
0.3040
0.4049
0.4575
0.4197
0.3972

270

-0.0557
-0.3997
-0.4178
-0.3445
0.0985
0.1 161
0.1 178
0.0173
0.0983

0.0335
0.4961
0.5047
0.5805
0.0935
0.2634
0.1264
0.1352
0.1617

B(eq)

9.4

5.6

5.6

5.6
7.8(3)
12.3(5)
16.1(7)
16.7(7)
7.2(7)

271

Table A.8. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

Pt(TMPP-0)2-3EtCN (1 9- 3EtCN).

 

 

atom x y z B(eq)
Pt( 1) 0.63277(3) 0.13964(1) 0.27018(2) 2.04(1)
P( 1) 0.7108(2) 0.15903(6) 0.1525(2) 2.1 1(9)
P(2) 0.7468(2) 0.10646(7) 0.3791(2) 2.3(1)
0(1) 0.4986(4) 0.1594(2) 0.1863(4) 2.7(3)
0(2) 0.3156(5) 0.1820(2) -0.1238(4) 4.2(3)
0(3) 0.6877(5) 0.1793(2) -0.0547(4) 3 .4(3)
0(4) 0.6291(5) 0.2451(2) 0.1154(5) 3.7(3)
0(5) 0.9516(6) 0.3133(2) 0.2414(5) 4.8(3)
0(6) 0.9246(4) 0.1709(2) 0.2527(4) 2.9(3)
0(7) 0.9065(5) 0.1729(2) 0.0559(4) 3 .3(3)
0(8) 0.9096(5) 0.0433(2) -0.0766(5) 4.9(4)
0(9) 0.6554(4) 0.0793(2) 0.1 134(4) 2.7(3)
O(10) 0.5331(4) 0.1344(2) 0.3628(3) 2.6(2)
0(1 1) 0.4774(5) 0.1081(2) 0.6679(4) 4.3(3)
O(12) 0.7950(5) 0.0690(2) 0.5746(4) 3.9(3)
O(13) 0.6158(6) 0.0316(2) 0.3895(5) 4.7(4)
0(14) 0.8153(7) -0.0621(2) 0.2546(5) 5 .8(4)
0(15) 0.9057(5) 0.0791(2) 0.2737(4) 3.3(3)
O(16) 0.9643(6) 0.0656(3) 0.4650(5) 5 .1(4)
0(17) 1.1483(8) 0.1787(4) 0.5970(8) 9.8(7)
0(18) 0.7768(6) 0.1871(2) 0.4288(5) 4.4(3)
C(l) 0.5942(6) 0.1676(2) 0.0657(5) 2.1(3)
C(2) 0.4992(6) 0.1657(2) 0.0970(6) 2.3(4)
C(3) 0.4035(7) 0.1719(3) 0.0356(6) 2.9(4)
C(4) 0.4041(7) 0.1782(3) -0.0566(6) 3.2(4) .
C(5) 0.4984(7) 0.1803(3) -0.0902(6) 2.8(4)
C(6) 0.5914(7) 0.1754(2) -0.0293(6) 2.5(4)
C(7) 0.7802(6) 0.2066(3) 0.1768(6) 2.5(4)
C(8) 0.7323(7) 0.2442(3) 0.1550(6) 2.8(4)
C(9) 0.7879(7) 0.2807(3) 0.1739(6) 2.9(4)
C( 10) 0.8912(8) 0.2794(3) 0.2187(6) 3 .4(5)
C(11) 0.9409(7) 0.2430(3) 0.2457(6) 3.5(5)
C(12) 0.8852(7) 0.2072(3) 0.2261(6) 2.7(4)
C(13) 0.7855(6) 0.1249(2) 0.0915(5) 2.0(3)
C(14) 0.8682(6) 0.1346(3) 0.0454(5) 2.7(4)
C(15) 0.9069(7) 0.1061(3) -0.0103(7) 3 .4(4)
C(16) 0.8649(7) 0.0687(3) -0.0198(6) 3 .2(4)

Table A.8. continued

atom

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)
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)
H(1)

H(2)

H(3)

X

0.7820(7)
0.7429(6)
0.6694(6)
0.5691(7)
0.5022(7)
0.5364(7)
0.6336(7)
0.6995(7)
0.7684(7)
0.7032(8)
0.7215(9)
0.8040(9)
0.8680(8)
0.8485(7)
0.8714(7)
0.9644(8)
1.048(1)
1.049(1)
0.961(1)
0.871 1(8)
0.2168(8)
0.6926(8)
0.5796(8)
0.907(1)
1.0332(8)
0.9940(8)
0.870(1)
0.6183(7)
0.3781(8)
0.8216(9)
0.540(1)
0.884(1)
0.9875(7)
1.066(1)
1.139(2)
0.772(1)
0.3391
0.4978
0.7548

272

Y

0.0576(3)
0.0862(3)
0.1048(3)
0.1209(2)
0.1228(3)
0. 1074(3)
0.0892(3)
0.0872(3)
0.0550(3)
0.0230(3)

-0.0156(3)
-0.0233(3)

0.0081(3)
0.0468(3)
0.1279(3)
0.1054(4)
0.1236(5)
0.1644(6)
0.1892(4)
0.1685(3)
0.1823(3)
0.1755(4)
0.2820(3)
0.3514(3)
0.1699(3)
0.1830(3)
0.0030(3)
0.0391(3)
0.1285(3)
0.0463(3)
0.0014(4)

-0.0697(4)

0.0721(3)
0.0463(5)
0.2168(5)
0.2299(3)
0.1716
0.1850
0.3056

Z

0.0212(6)
0.0755(6)
0.4702(6)
0.4462(6)
0.5122(6)
0.5988(6)
0.6232(6)
0.5595(6)
0.3413(6)
0.3537(6)
0.3245(6)
0.2800(6)
0.2626(7)
0.2922(6)
0.441 1(6)
0.4772(6)
0.5272(9)
0.5416(8)
0.5095(8)
0.4582(6)

-0.0942(8)
-0. 1500(7)

0.0853(7)
0.2127(8)
0.2960(7)
0.0153(8)

-0.0859(9)

0.] 166(6)
0.6477(7)
0.6564(8)
0.3936(8)
0.190(1)
0.2210(7)
0.4793(9)
0.604(1)
0.4232(8)
0.0577
-0. 1541
0.1560

Table A.8. continued

atom

mm

mm

mm

H(7)

mm

H®

mm)
mm)
ma)
mm)
mu)
mm)
mm)
H(17)
mm)
mm)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
my)
H(32)
H(33)
my)
H(35)
H(36)
H(37)
H(38)
mm)
mm)
ma)
mu)

X

1 .01 18
0.9623
0.7523
0.4344
0.6548
0.6767
0.9246
1.1075
0.9617
0.2148
0.1619
0.207 9
0.6673
0.6508
0.7635
0.5841
0.6136
0.5080
0.9560
0.8884
0.8454
1 .0537
1 .0747
1 .0433
1.0517
0.9765
1 .0121
0.7976
0.9080
0.8773
0.5585
0.5998
0.6720
0.3891
0.3359
0.3435
0.7717
0.8895
0.8217

273

0.2425
0.1 132
0.0314
0.1345
0.0782
-0.0370
0.0033
0.1079
0.2172
0.2041
0.1853
0.1577
0.1498
0.1958
0.1784
0.2997
0.2937
0.2772
0.3720
0.3521
0.3554
0.1430
0.1805
0.1857
0.1663
0.1790
0.2103
0.0035
-0.0121
-0.0091
0.0388
0.0289
0.0229
0.1560
0.1 166
0.1261
0.0254
0.0350
0.0632

0.2771
-0.0414
0.0129
0.4964
0.6834
0.3353
0.231 1
0.5533
0.521 1
-0.0527
-0. 1464
-0.0636
-0.1715
-0.1841
-0. 1578
0.1365
0.0398
0.0594
0.2335
0.1471
0.2386
0.31 1 1
0.2546
0.3508
0.0404
-0.0499
0.0278
-0.1 140
-0. 1233
-0.0264
0.1454
0.0555
0.1512
0.6360
0.5947
0.6991
0.6564
0.6596
0.7085

92
.3;

9999999999999999999
MNNNOOOVOOOOONWOOme-hr—H—

9999999
VIM-h-B-hUIUI

9N5"
mum

MMMPPPN
bohooou

999
MMM

Table A.8. continued

atom

H(43)
H(44)
H(45)
H(46)
H(47)
H(48)
H(49)
H(SO)
H(51)
H(52)
H(53)
H(54)
H(55)
H(56)
H(57)
H(58)
H(59)
H(60)
N(l)

C(53)
C(54)
C(55)
H(61)
H(62)
H(63)
H(64)
H(65)
N(3)

C(59)
C(60)
C(61)
H(66)
H(67)
H(68)
H(69)
H(70)
N(2)

C(56)
C(57)

X

0.4841
0.5140
0.5717
0.8847
0.8606
0.9534
1.0396
0.9583
1 .0184

. 1.0572

1.1063
1.1014
1.2119
1.0947
1.1245
0.7963
0.8156
0.7018

0.5887(8)

0.545(1)
0.490(1)
0.391(1)
0.5 370
0.4719
0.3574
0.3450
0.4085

0. 1880(9)

0.253(1)
0.336(1)
0.302(1)
0.3719
0.3822
0.2673
0.2557
0.3620
0.257(1)
0.321(1)
0.414(1)

274

Y

0.0124
-0.0083
-0.0200
-0.0977
-0.0553
-0.0613
0.0551
0.0596
0.0970
0.0182
0.0571
0.0508
0.2285
0.2279
0.2245
0.241 1
0.2391
0.2381
0.0183(3)
0.0443(4)
0.0786(4)
0.0679(4)
0.0916
0.0966
0.0918
0.0534
0.0518
0.0994(4)
0.0942(4)
0.0864(5)
0.0802(5)
0.0630
0.1087
0.1036
0.0579
0.0750
0.2069(8)
0.2124(7)
0.2196(5)

Z

0.4192
0.3331
0.4317
0.1773
0.1348
0.2169
0.2552
0.1639
0.2092
0.4688
0.4373
0.5410
0.6020
0.5539
0.6608
0.4829
0.3819
0.4011

0.8415(8)
0.8625(8)

0.894(1)
0.929(1)
0.9424
0.8432
0.9436
0.8829
0.9832
0.083(1)
0.143(1)
0.222(1)
0.310(1)
0.2082
0.2281
0.3259
0.3054
0.3568
0.408(2)
0.376(2)
0.337(1)

B(eq)

8.4
8.4
8.4
10.3
10.3
10.3
4.9
4.9
4.9
9.9
9.9
9.9
14.0
14.0
14.0
7.2
7.2
7.2
6.4(6)
5.5(7)
8.3(8)
8.7(9)
9.9
9.9
10.5
10.5
10.5
8.6(8)
6.6(8)
8.0(9)
10( 1)
9.6
9.6
11.9
11.9
11.9
22(2)
11(1)
9(1)

Table A.8. continued

atom

C(58)
H(71)
H(72)
H(73)
H(74)
H(75)

X

0.395(2)

0.4579
0.4486
0.4596
0.3558
0.3555

275

Y

0.2367(6)

0.2374
0.1946
0.2422
0.2180
0.2607

Z

0.246(1)

0.3767
0.3341
0.2281
0.2040
0.2465

B(eq)

18(2)
10.3
10.3
22.5
22.5
22.5

276

Table A.9. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
Cd(N03)2(TMPP) (2 1).

 

 

atom x y z B(eq)
Cd(l) 0.80572(7) 0.1460(1) 0.6149 2.12(4)
P(l) 0.8358(3) 0.0224(4) 0.7170(3) 1.7(2)
0(1) 0.8065(9) 0.245(1) 0.7577(7) 3.1(6)
0(2) 1.041 1(9) 0.297(1) 0.9285(8) 4.2(7)
0(3) 0.9932(8) -0.059(1) 0.8082(7) 3.1(6)
0(4) 0.8074(8) -0.091(1) 0.8544(6) 2.8(6)
0(5) 0.4895(7) -0.053( 1) 0.8641(7) 3.1(6)
0(6) 0.6561(7) 0.079(1) 0.6644(6) 2.4(5)
0(7) 0.805(1) -0.236(1) 0.7286(8) 4.0(7)
O(8) 1.058(1) -0.351(1) 0.600(1) 4.8(8)
0(9) 0.9843(7) 0.042(1) 0.626(1) 3.5(7)
0(1 1) 0.7245(8) 0.120(1) 0.5106(7) 3.4(7)
O(12) 0.847(1) 0.027(2) 0.506(1) 6(1)
O(13) 0.752(1) 0.009(1) 0.4209(8) 4.9(8)
0(21) 0.886(1) 0.299(1) 0.5768(8) 4.1(7)
0(22) 0.7523(8) 0.329(1) 0.6029(9) 3.0(7)
0(23) 0.835(1) 0.470(1) 0.574(1) 6(1)
N(l) 0.771(1) 0.052(2) 0.4785(9) 3.2(9)
N(2) 0.822(1) 0.369(1) 0.5843(8) 3.4(9)
C(19) 0.773(2) 0.356(2) 0.775(1) 5(1)
C(20) 1.121(1) 0.264(2) 0.961(1) 5(1)
C(21) 1.061(1) -0.113(2) 0.844(2) 6(1)
C(22) 0.806(2) -0. 149(3) 0.923(1) 7(2)
C(23) 0.485(1) -0.087(2) 0.939(1) 4(1)
C(24) 0.574(1) 0.1 19(2) 0.6346(8) 3(1)
C(25) 0.788(2) -0.346(2) 0.747(2) 9(2)
C(26) 1.134(1) -0.326(2) 0.560(1) 5(1)
C(27) 1.048(2) 0.071(2) 0.571(1) 6(1)
H(1) 0.9197 0.3502 0.8551 3.8
H(2) 1 .0729 0.0827 0.8979 3.3
H(3) 0.6430 -0. 1089 0.9119 4.3
H(4) 0.5139 0.0328 0.7442 2.3
H(5) 0.9218 -0.3713 0.6694 3.6
H(6) 1.0802 -0.1348 0.5846 3.7
H(7) 0.8179 0.4102 0.7667 6.4
H(8) 0.7229 0.3723 0.7455 6.4
H(9) 0.7557 0.3583 0.8246 6.4

Table A.9. continued

atom

H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
H(31)
H(32)
H(33)
C(1)

C(2)

C(3)

C(4)

C(5)

C(6)

C(7)

C(8)

C(9)

C(10)
C(11)
C(12)
C(13)
C(14)
C(15)

X

1.1 121
1.1647
1.1413
1 .0492
1 .0668
1.1 153
0.7810
0.7706
0.8645
0.4253
0.5177
0.5109
0.5481
0.5850
0.5344
0.7322
0.7846
0.8333
1.1643
1.1 188
1.1737
1.1042
1 .0287
1.0543
0.9032(7)
0.8787(6)
0.9267(8)
0.9992(7)
1.0236(6)
0.9756(8)
0.7298(6)
0.7300(6)
0.6503(7)
0.5705(6)
0.5704(6)
0.6500(7)
0.8965(8)
0.8769(7)
0.9323(8)

277

Y

0.1959
0.2507
0.3204
-0.1 138
-0.1872
-0.0732
-0. 1005
-0.2144
-0.1684
-0.0976
-0. 1542
-0.0293
0.1722
0.1542
0.0580
-0.351 1
-0.3909
-0.3745
-0.3930
-0.2852
-0.2808
0.0383
0.0427
0.1500
0.0956(9)
0.207(1)
0.2719(7)
0.2258(8)
0.1 146(9)
0.0495(7)
-0.009(1)
-0.059(1)
-0.075(1)
-0.040(1)
0.01 1(1)
0.026(1)

-0.0984(9)

-0.211(1)

-0.2945 (7)

Z

0.9876
0.9246
0.9929
0.8943
0.8264
0.8354
0.9590
0.9193
0.9367
0.9526
0.9454
0.9683
0.6668
0.5892
0.6280
0.7716
0.7041
0.7773
0.5460
0.5170
0.5880
0.5824
0.5253
0.5680
0.7845(6)
0.7971(6)
0.8461(7)
0.8826(6)
0.8700(6)
0.8210(6)
0.7598(6)
0.8280(6)
0.8653(5)
0.8343(6)
0.7661(6)
0.7288(5)
0.6797(7)
0.6919(6)
0.6640(7)

5.7

w?”3":“:“9°9°.°°>'>‘>‘
umoooooooxmar—r—r—

v—w
Ob,‘
\1

10.7
10.7
6.6
6.6
6.6
6.7
6.7
6.7
2.5(1)
2.5(1)
2.5(1)
2.5(1)
2.5(1)
2.5(1)
2.3(1)
2.3(1)
2.3(1)
2.3(1)
2.3(1)
2.3(1)
3.0(1)
3.0(1)
3.0(1)

Table A.9. continued

atom x

C(16) 1.0072(7)
C(17) 1.0268(6)
C(18) 0.9715(8)

278

y 2
-0.2650(8) 0.6239(7)
-0.152(1) 0.6118(7)
-0.0689(7) 0.6396(7)

B(eq)
3.0(1)
3.0(1)
3.0(1)

 

279

Table A.10. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[PPh412 [F6206] (2 5).

 

 

atom x y z B(eq)
Fe( 1) 0.13606(4) 0.45620(3) 0.08785(4) 1.98(1)
Cl(1) 0.36021 (7) 0.58005(5) 0.19160(7) 264(2)
Cl(2) -0.05489(7) 0.51691 (5) 0.15200(6) 2.24(2)
Cl(3) 0.09172(7) 0.27727(5) 0.11055(7) 265(2)
P( 1) 0.81269(7) 0.16670(5) 0.44836(6) 1.57(2)
C( 1) 0.6844(2) 0.2273(2) 0.3651(2) 1.72(7)
C(2) 0.5805(3) 0.2509(2) 0.4318(3) 2.21(8)
C(3) 0.4858(3) 0.2978(2) 0.3585(3) 2.9(1)
C(4) 0.4956(3) 0.3241(2) 0.2243(3) 2.8(1)
C(5) 0.6002(3) 0.3026(2) 0.1595(3) 250(9)
C(6) 0.6933(3) 0.2531(2) 0.2282(3) 2.24(8)
C(7) 0.7700(2) 0.1227(2) 0.6126(2) 1.76(7)
C(8) 0.7875(3) 0.2057(2) 0.7222(3) 233(8)
C(9) 0.7621(3) 0.1790(2) 0.8535(3) 2.49(9)
C(10) 0.7187(3) 0.0703(2) 0.8761(3) 2.41 (9)
C(11) 0.7013(3) -0.0119(2) 0.7691(3) 2.45(9)
C(12) 0.7268(3) 0.0136(2) 0.6360(3) 2.14(8)
C( 13) 0.7990(3) 0.0516(2) 0.3242(2) 1.78(7)
C(14) 0.6615(3) -0.0304(2) 0.2773(3) 2.18(8)
C(15) 0.6447(3) -0.1184(2) 0.1775(3) 2.47(9)
C(16) 0.7636(3) -0. 1247(2) 0.1232(3) 2.51 (9)
C(17) 0.8995(3) -0.0433(2) 0.1668(3) 2.44(9)
C(18) 0.9187(3) 0.0461(2) 0.2687(3) 2.01 (8)
C(19) 0.9951(3) 0.2658(2) 0.4924(2) 1.77(7)
C(20) 1.1043(3) 0.2388(2) 0.5797(3) 2.8(1)
C(21) 1.2454(3) 0.3152(2) 0.6196(3) 3.1(1)
C(22) 1.2786(3) 0.4161(2) 0.5718(3) 252(9)
C(23) 1.1710(3) 0.4420(2) 0.4847(3) 2.41(9)
C(24) 1 .0283 (3) 0.3674(2) 0.4443(3) 2.03(8)
H(1) 0.582(3) 0.234(2) 0.515(3) 2.3(6)
H(2) 0.412(4) 0.309(3) 0.399(4) 4.5(8)
H(3) 0.423(3) 0.355(2) 0.170(3) 2.3(6)
H(4) 0.613(3) 0.321(3) 0.061(4) 4.0(7)
H(5) 0.764(3) 0.240(2) 0.183(3) 3.0(6)
H(6) 0.809(3) 0.278(2) 0.712(3) 2.7(6)
H(7) 0.766(3) 0.233(3) 0.929(3) 3.3(7)

H(8)

0.698(3)

0.052(2)

0.967(3)

3.1(6)

Table A.10. continued

280

atom x y z B(eq)
H(9) 0.678(3) -0.089(2) 0.795(3) 2.0(5)
H(10) 0.713(3) -0.041(2) 0.569(3) 1.6(5)
H(11) 0.578(3) -0.026(2) 0.318(3) 1.9(5)
H(12) 0.548(3) -0. 173(2) 0.149(3) 2.0(5)
H(13) 0.762(3) —0. 180(2) 0.051(3) 2.1(5)
H(14) 0.979(3) -0.049(2) 0.129(3) 3 .0(6)
H(15) 1.021(3) 0.104(2) 0.301(3) 1.7(5)
H(16) 1.082(3) 0.165(3) 0.616(3) 4.1(7)
H(17) 1.320(4) 0.291(3) 0.681(4) 4.4(8)
H(18) 1.379(3) 0.468(2) 0.603(3) 2.5(6)
H(l9) 1.191(3) 0.504(3) 0.449(3) 3.3(7)
H(20) 0.951 (3) 0.388(2) 0.379(3) 3.1(6)

 

281

Table A.11. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[Et4Nl2lF62Cl6] (2 6).

 

 

atom x y z B(eq)
Fe( 1) -0.07374(4) 0.1 1261(4) 0.06084(2) 2.24(2)
Cl(1) 0.01682(9) 0.12277(8) 0.20921 (5) 324(3)
Cl(3) -0.26255(8) 0.25636(7) -0.00140(5) 3.33(3)
Cl(2) 0.14098(8) 0.10682(6) -0.00951(5) 2.61 (3)
N(1) 0.5530(2) 0.0808(2) 0.2758(1) 1.95(8)
C(l) 0.7068(3) 0.0174(3) 0.3247(2) 2.1(1)
C(2) 0.7993(4) 0.0900(3) 0.4049(2) 3 . 1 (1)
C(3) 0.4740(3) -0.0082(3) 0.1991(2) 2.3(1)
C(4) 0.5588(4) -0.0194(3) 0.1263(2) 3.1(1)
C(5) 0.4423(3) 0.0992(3) 0.3364(2) 2.6(1)
C(6) 0.4069(4) -0.0232(4) 0.3814(2) 3.5(1)
C(7) 0.5903(3) 0.2143(3) 0.2425(2) 2.6(1)
C(8) 0.4510(4) 0.2820(4) 0.1831(3) 4.1(2)
H(l 1) 0.682(3) -0.068(3) 0.344(2) 1.9(5)
H(12) 0.772(3) 0.006(2) 0.282(2) 1.6(5)
H(21) 0.886(4) 0.029(3) 0.430(2) 4.9(8)
H(22) 0.830(4) 0.171(4) 0.392(2) 4.8(9)
H(23) 0.734(5) 0.104(4) 0.448(3) 7(1)
H(31) 0.459(3) -0.092(3) 0.226(2) 2.5(6)
H(32) 0.379(4) 0.022(3) 0.180(2) 2.4(6)
H(41) 0.666(4) -0.045(3) 0.147(2) 3.9(7)
H(42) 0.505(4) -0.084(3) 0.087(2) 2.4(6)
H(43) 0.566(4) 0.066(3) 0.096(2) 3 .7(7)
H(51) 0.489(3) 0.160(3) 0.376(2) 1.7(5)
H(52) 0.337(4) 0.129(3) 0.297(2) 4.2(7)
H(61) 0.330(4) -0.003(3) 0.410(2) 4.6(8)
H(62) 0.354(4) -0.093(3) 0.337(2) 4.3(8)
H(63) 0.503(5) -0.065(4) 0.426(3) 5 .7(9)
H(71) 0.627(4) 0.265(3) 0.293(2) 2.7(6)
H(72) 0.668(3) 0.204(3) 0.208(2) 2.6(6)
H(81) 0.491(4) 0.366(4) 0.165(2) 4.8(8)
H(82) 0.427(6) 0.249(5) 0.130(3) 9(1)

H(83)

0.371(7)

0.298(5)

0.214(3)

10( 1)

 

282

Table A.12. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[ppn]2[F62Cl6] (2 7) .

 

 

atom x y z B(eq)
Fe( 1) 0.0669(1) -0.0676(2) 0.0314(1) 2.0(1)
Fe(2) 0.5590(1) 0.0397(2) 0.0533(1) 2.0(1)
Cl(1) 0.1364(3) 0.0043(4) 0.1039(2) 4.0(3)
Cl(2) -0.0392(2) -0.0478(4) 0.0471(2) 3 .1(3)
Cl(3) 0.0827(2) -0.227 4(4) 0.0045(2) 2.4(2)
Cl(4) 0.6328(3) 0.1429(4) 0.0324(2) 2.9(3)
Cl(5) 0.4595(2) 0.1100(4) 0.0042(2) 2.3(2)
Cl(6) 0.5643(2) -0.0076(4) 0.1449(2) 3.0(2)
P( 1) 0.2178(2) 0.5130(4) 0.1482(2) 1.6(2)
P(2) 0.1251(2) 0.5149(4) 0.2225(2) 1.5(2)
P(3) 0.6253(2) 0.5849(4) 0.2048(2) 1.4(2)
P(4) 0.7080(2) 0.6153(4) 0.1211(2) 1.6(2)
N (1) 0.1868(6) 0.547(1) 0.2008(6) 1.7(7)
N(2) 0.6757(6) 0.637(1) 0.1736(6) 1.5(3)
C(l) 0.2389(7) 0.626(1) 0.1151(6) 0.3(3)
C(2) 0.2573(8) 0.624(1) 0.0632(7) 1.5(4)
C(3) 0.2699(8) 0.710(1) 0.0369(7) 1.2(8)
C(4) 0.263(1) 0.804(2) 0.0600(9) 3(1)

C(5) 0.2483(8) 0.811(1) 0.1134(8) 1.6(4)
C(6) 0.2355(8) 0.721(1) 0.1415(7) 1.3(4)
C(7) 0.2894(8) 0.442(1) 0.1754(8) 1.7(8)
C(8) 0.322(1) 0.391(2) 0.137(1) 3(1)

C(9) 0.377(1) 0.342(1) 0.161(1) 2(1)

C(10) 0.402(1) 0.337(2) 0.219(1) 2.9(5)
C(11) 0.371(1) 0.386(2) 0.2556(9) 3(1)

C(12) 0.314(1) 0.435(2) 0.2327(8) 2.3(4)
C(13) 0.1682(8) 0.443(1) 0.0918(7) 1.2(4)
C(14) 0.124(1) 0.491(2) 0.0498(9) 3(1)

C(15) 0.083(1) 0.437(2) 0.008(1) 4(1)

C(16) 0.083(1) 0.329(2) 0.0125(9) 2(1)

C(17) 0.127(1) 0.283(2) 0.055(1) 3(1)

C(18) 0.1667(9) 0.337(1) 0.0941(8) 1.4(9)
C(19) 0.0586(8) 0.597(1) 0.1945(7) 1.2(8)
C(20) 0.065(1) 0.673(1) 0.1553(8) 1.7(4)
C(21) 0.015(1) 0.735(2) 0.137(1) 4(1)

C(22) -0.042(1) 0.728(2) 0.1549(9) 3(1)

C(23) -0.048(1) 0.652(2) 0.1926(9) 3(1)

Table A. 12. continued

atom

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)
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)
C(56)
C(57)
C(58)
C(59)
C(60)
C(61)
C(62)

X

0.0032(8)
0.1452(8)
0.1943(9)
0.207(1)
0.168(1)
0.1 18(1)
0.1031(9)
0.098(1)
0.044(1)
0.028(1)
0.066(1)
0.1 18(1)
0.135(1)
0.6235(8)
0.5881(8)
0.591(1)
0.628(1)
0.662(1)
0.6603(8)
0.5462(9)
0.5349(9)
0.475(1)
0.425(1)
0.434(1)
0.495(1)
0.6472(8)
0.704(1)
0.725(1)
0.684(1)
0.625(1)
0.6050(9)
0.7343(8)
0.7799(9)
0.796(1)
0.770(1)
0.729(1)
0.71 14(9)
0.6543(8)
0.617(1)

283

Y

0.589(1)
0.531(1)
0.589( 1)
0.601(2)
0.561(2)
0.501(2)
0.485(2)
0.383(1)
0.370(1)
0.272(2)
0.195(2)
0.206(2)
0.306(1)
0.449(1)
0.398(1)
0.294(2)
0.244(2)
0.288(2)
0.394(1)
0.625(1)
0.714(1)
0.746(1)
0.702(2)
0.616(2)
0.578(2)
0.622(1)
0.668(1)
0.696(1)
0.676(2)
0.629(2)
0.604(1)
0.737(1)
0.748(1)
0.839(2)
0.923(1)
0.920(2)
0.824(1)
0.570(1)
0.634(1)

Z

0.2136(7)
0.2991(7)
0.3253(8)
0.384(1)

0.4172(8)
0.390(1)

0.3310(7)
0.2059(8)
0.1615(8)
0.147(1)

0.175(1)

0.2164(9)
0.2332(8)
0.2039(7)
0.1578(7)
0.1544(9)
0.200(1)

0.2467(8)
0.2491(7)
0.1738(8)
0.1405(8)
0.1215(8)
0.136(1)

0.168(1)

0.1894(8)
0.2796(7)
0.3004(8)
0.3600(8)
0.3958(8)
0.3741(8)
0.3162(8)
0.1027(7)
0.0680(8)
0.0515(9)
0.0676(8)
0.1035(9)
0.1214(8)
0.0578(8)
0.0222(9)

B(eq)

1.4(8)
1.6(4)
2.2(4)
3(1)
3(1)
3(1)
2(1)
1.7(4)
2(1)
4(1)
3(1)
2(1)
2(1)
1.2(4)
1.3(4)
2.5(5)
4(1)
2(1)
1.3(4)
1.6(4)
1.6(9)
2(1)
3(1)
3(1)
2(1)
1.3(8)
2.1(4)
3(1)
3(1)
2.4(4)
2.0(4)
0.7(3)
2(1)
3(1)
2(1)
2.5(4)
2(1)
1.5(4)
3(1)

Table A.12. continued

atom

C(63)
C(64)
C(65)
C(66)
C(67)
C(68)
C(69)
C(70)
C(71)
C(72)
H(1)

H(2)

H(3)

H(4)

H(5)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)

X

0.568(1)
0.563(1)
0.6034(9)
0.6499(9)
0.7737(8)
0.7959(8)
0.8480(9)
0.8779(9)
0.851(1)
0.8027(8)
0.261 1
0.2836
0.2691
0.2464
0.2250
0.3059
0.3997
0.4399
0.3884
0.2914
0.1228
0.0548
0.0540
0.1286
0.1952
0.1027
0.0189
-0.0745
-0.0874
-0.0004
0.2199
0.2445
0.1764
0.0916
0.0674
0.0206
-0.0079
0.0544
0.1417

284

Y

0.599(2)
0.496(2)
0.428(2)
0.462(1)
0.530(1)
0.508(1)
0.441(1)
0.400(1)
0.424(1)
0.488(1)
0.5608
0.7053
0.8640
0.8753
0.7243
0.3917
0.3091
0.3005
0.3856
0.4662
0.5623
0.4706
0.2892
0.21 14
0.3028
0.681 1
0.7852
0.7759
0.6429
0.5399
0.6206
0.6383
0.5732
0.4705
0.4458
0.4253
0.2573
0.1283
0.1494

Z

-0.0247(8)
-0.0328(8)
0.0035(8)
0.0506(8)
0.1396(7)
0.1969(7)
0.2123(8)
0.171(1)
0.1 102(8)
0.0980(7)
0.0457
0.0016
0.0394
0.131 1
0.1780
0.0970
0.1355
0.2334
0.2956
0.2584
0.0496
-0.0224
-0.0137
0.0576
0.1243
0.1422
0.1093
0.1419
0.2035
0.2417
0.3029
0.4014
0.4572
0.4128
0.3126
0.1425
0.1 174
0.1630
0.2340

B(eq)

2.5(4)
2.5(4)
2( 1)

1.9(4)
1.8(9)
1.2(4)
2(1)

3(1)

2.3(4)
1 1(3)

NPPPPPPPwaPPPEPPPPPPPPPfPPFH
«maummmqaqomwoqmmmqmoh~maoomq

Table A.12. continued

atom

H(30)
H(31)
H(32)
H(33)
H(34)
H(35)
H(36)
H(37)
H(38)
H(39)
H(40)
H(41)
H(42)
H(43)
H(44)
H (45)
H(46)
H(47)
H(48)
H(49)
H(50)
H(51)
H(52)
H (53)
H(54)
H(55)
H(56)
H (57)
H(5 8)
H(59)
H(60)

X

0.1715
0.5613
0.5687
0.6274
0.6873
0.6845
0.5693
0.4675
0.3836
0.3981
0.5022
0.7304
0.7652
0.6956
0.5985
0.5642
0.7987
0.8271
0.7798
0.7125
0.6837
0.6230
0.5415
0.5323
0.5995
0.6768
0.7769
0.8633
0.9136
0.8674
0.7861

285

0.3200
0.4359
0.2588
0.1735
0.2492
0.4279
0.751 1
0.8019
0.7313
0.581 1
0.5206
0.6819
0.7260
0.6931
0.6152
0.5766
0.6887
0.8449
0.9872
0.9801
0.8206
0.7040
0.6454
0.4690
0.3575
0.4172
0.5369
0.4232
0.3580
0.3954
0.5071

0.2623
0.1280
0.1213
0.1980
0.2767
0.2818
0.1318
0.0960
0.1242
0.1761
0.2141
0.2747
0.3739
0.4353
0.3998
0.3018
0.0560
0.0286
0.0536
0.1 160
0.1472
0.0283

-0.0486
-0.0640
-0.0032

0.0760
0.2257
0.2513
0.1809
0.0803
0.0590

2.0

:‘P’PNT‘PPP’PPPPNPNPPPPPNP’PP
hNHQ-h-FQHNH-AHQHAwHNNmmmoa

286

Table A.13. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[AsPh412 [F6206] (2 8).

 

 

atom x y z B(eq)
Fe(l) 0.13314(6) 0.45543 (5) 0.08629(6) l.89(2)
Cl(1) 0.3570(1) 0.5772(1) 0.1872(1) 266(4)
Cl(2) -0.0545( 1) 051908(9) 0.1520(1) 2.21 (4)
Cl(3) 0.0833(1) 0.27768(9) 0.1113(1) 254(4)
As(1) 0.81238(4) 0.16721(3) 0.45032(4) 1.42(1)
C(l) 0.6767(4) 0.2314(3) 0.3614(4) 15(1)
C(2) 0.5697(5) 0.2508(3) 0.4257(5) 2.0(2)
C(3) 0.4736(5) 0.2955(4) 0.3545(5) 2.7(2)
C(4) 0.4868(5) 0.3228(4) 0.2222(6) 2.7(2)
C(5) 0.5942(5) 0.3052(4) 0.1603(5) 2.5(2)
C(6) 0.6901(5) 0.2584(4) 0.2275(4) 2.1(2)
C(7) 0.7642(4) 0.1215(3) 0.6240(4) 1.6(1)
C(8) 0.7804(5) 0.2042(4) 0.7307(4) 2.1(2)
C(9) 0.7527(5) 0.1768(4) 0.8610(5) 2.4(2)
C(10) 0.7104(5) 0.0694(4) 0.8855(5) 2.2(2)
C(l 1) 0.6949(5) -0.0123(4) 0.7781(5) 2.4(2)
C(12) 0.721 1(5) 0.0130(4) 0.6476(5) 2.0(2)
C(13) 0.8004(4) 0.0457(3) 0.3206(4) 1.4(1)
C(14) 0.6644(5) -0.0366(3) 0.2763(4) 2.0(2)
C(15) 0.6495(5) -0. 1231(4) 0.1770(5) 2.3(2)
C(16) 0.7694(5) -0. 1271(4) 0.1220(5) 2.3(2)
C(17) 0.9043(5) -0.0447(4) 0.1651(5) 2.3(2)
C(18) 0.9203(5) 0.0418(4) 0.2647(4) 1.9(1)
C(19) 1.0054(4) 0.2725(3) 0.4967(4) 1.6(1)
C(20) 1.1 133(5) 0.2477(4) 0.5859(5) 2.8(2)
C(21) 1.2532(5) 0.3244(4) 0.6245(6) 3.1(2)
C(22) 1.2853(5) 0.4223(4) 0.5749(5) 2.4(2)
C(23) 1.1795(5) 0.4469(4) 0.4867(5) 2 .4(2)
C(24) 1 0379(5) 0.3720(3) 0.4469(5) 2.0(1)
H(1) 0.561(4) 0.234(3) 0.509(4) 1.5(8)
H(2) 0.396(5) 0.309(3) 0.400(4) 3(1)
H(3) 0.432(6) 0.351(4) 0.179(5) 4(1)
H(4) 0.601(5) 0.318(4) 0.087(5) 2(1)
H(5) 0.774(4) 0.250(3) 0.184(4) 1.2(8)
H(6) 0.813(4) 0.282(3) 0.717(4) 1.5(8)
H(7) 0.766(5) 0.224(4) 0.937(5) 4(1)

H(8)

0.685(5)

0.050(3)

0.978(4)

25(9)

Table A.13. continued

287

atom x y z B(eq)
H(9) 0.667(5) -0.087(4) 0.796(5) 3(1)
H(10) 0.713(5) -0.043(4) 0.582(4) 2.1(9)
H(11) 0.581(4) -0.033(3) 0.313(4) 1.5(8)
H(12) 0.568(5) -0.174(4) 0.143(4) 2(1)
H(13) 0.762(4) -0.182(3) 0.054(4) 1.2(8)
H(14) 0.986(5) -0.035(4) 0.120(5) 3 ( 1)
H(15) 1.001(5) 0.102(3) 0.281(4) 1.4(8)
H(16) 1.083(5) 0.177(4) 0.614(5) 3(1)
H(17) 1.314(6) 0.310(4) 0.679(5) 4(1)
H(18) 1.379(5) 0.469(4) 0.596(4) 2(1)
H(19) 1.199(5) 0.515(4) 0.458(4) 2(1)
HLZQ 0.963(4) 0.391(3) 0.390(4) 1.4(8)

 

288

Table A.14. Atomic positional parameters and equivalent isotropic

displacement parameters (A2) and their estimated standard deviations for

[13th312 [F604] (3 0) -

 

 

atom x y z B(eq)
Fe(1) 0.25257(4) -0.00465(5) 0.17666(4) 1.80(3)
Cl(1) 0.13676(8) 0.1297(1) 0.14286(6) 2.31(5)
Cl(2) 0.22328(7) -0. 1793(1) 0.233890) 242(5)
Cl(3) 0.35309(8) 0.0857(1) 0.27889(6) 2.24(5)
Cl(4) 0.29833(8) -0.0421(1) 0.05718(7) 274(5)
N( 1) 0.4843(2) 0.2508(3) 0.1067(2) 1.9(2)
C( 1) 0.5029(3) 0.1257(4) 0.1328(3) 2.5(2)
C(2) 0.6013(3) 0.0897(4) 0.1425(3) 2.8(2)
C(3) 0.5350(3) 0.3342(4) 0.1669(3) 2.5(2)
C(4) 0.5221(3) 0.3154(4) 0.2510(3) 2.8(2)
C(5) 0.5151(3) 0.2736(4) 0.0299(3) 2.5(2)
C(6) 0.4774(4) 0.1936(5) -0.0377(3) 3.3(2)
C(7) 0.3810(3) 0.2690(4) 0.0978(3) 2.4(2)
C(8) 0.3486(3) 0.3900(4) 0.0754(3) 2.1(2)
C(9) 0.3342(3) 0.4687(4) 0.1325(3) 2.9(2)
C(10) 0.3041(3) 0.5803(5) 0.1124(3) 3 .4(2)
C(l 1) 0.2859(3) 0.6140(4) 0.0345(4) 3.4(2)
C(12) 0.2991(3) 0.5372(4) -0.0238(3) 3.1(2)
C(13) 0.3303(3) 0.4263(4) -0.0030(3) 2.5(2)
N(2) 0.0868(2) 0.1629(3) 0.8617(2) 1.8(1)
C(14) 0.0667(3) 0.1697(4) 0.9448(2) 2.4(2)
C(15) -0.0294(4) 0.1398(4) 0.9515(3) 2.8(2)
C(16) 0.0618(3) 0.0452(4) 0.8248(2) 1.9(2)
C(17) 0.1 170(3) -0.0557(4) 0.8652(3) 2.6(2)
C(18) 0.1877(3) 0.1848(4) 0.8691(3) 2.5(2)
C(19) 0.2264(3) 0.1626(4) 0.7964(3) 3.1(2)
C(20) 0.0308(3) 0.2524(4) 0.8075(2) 1 .7(2)
C(21) 0.0243(3) 0.3724(4) 0.8410(2) 1.7(2)
C(22) -0.0565(3) 0.4060(4) 0.8657(3) 2.1(2)
C(23) -0.0661(3) 0.5168(4) 0.8930(3) 2.5(2)
C(24) 0.0035(3) 0.5970(4) 0.8955 (3) 2.6(2)
C(25) 0.0815(3) 0.5663(4) 0.8691(3) 2.4(2)
C(26) 0.0917(3) 0.4544(4) 0.8421(2) 2.0(2)
H(1) 0.4837 0.1143 0.1818 3.0
H(2) 0.4680 0.0758 0.0942 3.0
H(3) 0.6073 0.0103 0.1583 3.3
H(4) 0.6212 0.0988 0.0940 3.3

Table A.14. continued

atom

H(5)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
H(31)
H(32)
H(33)
H(34)
H(35)
H(36)
H(37)
H(38)
H(39)
H(40)
H(41)
H(42)
H(43)

X

0.6367
0.5986
0.5158
0.5560
0.4596
0.5420
0.4977
0.5799
0.4137
0.5012
0.4957
0.3515
0.3640
0.3460
0.2965
0.2632
0.2866
0.3394
0.1058
0.0775
-0.0367
-0.0702
-0.0421
-0.0015
0.0693
0.1085
0.0967
0.1789
0.1989
0.2187
0.2158
0.1957
0.2888
0.0557
-0.0302
-0. 1053
-0.1204
-0.0035
0.1283

289

0.1363
0.3290
0.41 19
0.3714
0.3235
0.2401
0.3512
0.2693
0.1974
0.2138
0.1 153
0.2158
0.2490
0.4455
0.6356
0.6910
0.5608
0.3728
0.1 178
0.2465
0.1447
0.1903
0.0615
0.0320
0.0483

-0.0604
-0. 1266
-0.0447

0.2638
0.1361
0.0835
0.21 10
0.1782
0.2593
0.2222
0.3510
0.5381
0.6749
0.6237

0.1817
0.1662
0.1518
0.2855
0.2539
0.2682
0.0134
0.0387

-0.0497
-0.0841
-0.0241

0.0586
0.1470
0.1877
0.1523
0.0205

-0.0783
-0.0437

0.9781
0.9641
1.0048
0.9199
0.9335
0.8249
0.7708
0.9189
0.8395
0.8644
0.8855
0.91 12
0.7800
0.7541
0.8047
0.7605
0.7920
0.8626
0.91 14
0.9145
0.8689

B(eq)

.9"
w

PPSQPPNPPPPPPPPPPPPWPPPPPPPPPPWPPPPPWPN
m~ow-mumoc-NwwwwummomwmwocOOOOObhhoc

290

Table A.14. continued

atom x y z B(eq)
H(44) 0.1466 0.4333 0.8245 2.3

 

291

Table A.15. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
Fe4C13(THF)6 (3 3).

 

 

atom x y z B(eq)
Fe( 1) -0.22350(5) -0.07907(5) -0.20584(5) 215(3)
Fe(2) 0.07954(4) -0.18501(5) 0.01669(4) 1.90(3)
Cl(1) -0.3111(1) 0.1745(1) -0.0761(1) 300(5)
Cl(2) -0. 1915(1) -0. 1888(1) -0.4495(1) 3.79(6)
Cl(3) —0. 1457 8(9) -0.2097(1) -0.04340(9) 256(4)
Cl(4) -0.03564(8) 0.08025(8) 0.17935(8) 208(4)
0( 1) -0.4354(2) -0.0605(3) -0.2029(3) 3.2(1)
0(2) 0.1917(3) -0.4074(3) -0. 1237(2) 3.2(1)
0(3) 0.0998(3) -0.2611(3) 0.1888(2) 2.9(1)
C( 1) -0.5501(4) 0.0254(5) -0.2752(5) 4.3(2)
C(2) 0.6287(6) -0.0647(6) -0.3491(6) 6.6(4)
C(3) -0.5858(5) -0. 1778(5) -0.2847(5) 4.7(3)
C(4) -0.4716(5) -0. 1666(5) -0. 1878(5) 4.8(3)
C(5) 0.1731(4) -0.4613(4) -0.2788(4) 3.1(2)
C(6) 0.3180(4) -0.5228(5) -0.3480(4) 4.0(2)
C(7) 0.4221(4) -0.5536(5) -0.2304(5) 4.8(3)
C(8) 0.3294(4) -0.5138(4) -0.1021(4) 3.9(2)
C(9) 0.0676(5) -0.3757(5) 0.1913(4) 4.0(3)
C(10) 0.1515(5) -0.4230(4) 0.3106(5) 4.2(3)
C(l 1) 0.1777(4) -0.2934(4) 0.4109(4) 35(2)
C(12) 0.1 125(5) -0.1804(4) 0.3397(4) 3.4(2)
H(1) -0.6120 0.1162 -0.2066 5 .3
H(2) -0.5123 0.0437 -0.3440 5.3
H(3) -0.7294 -0.0048 0.3344 8.0
H(4) -0.6049 -0.1080 -0.4504 8.0
H(5) —0.6645 -0. 1637 -0.2330 5.6
H(6) -0.5515 -0.2730 -0.3593 5 .6
H(7) -0.3899 -0.2589 -0.21 16 5.8
H(8) -05034 -0. 1364 ~0.0902 5.8
H(9) 0.1405 -0.5353 -0.3034 3.8
H(10) 0.1059 -0.3833 -0.3091 3.8
H(l 1) 0.3361 -0.6106 -0.4287 4.8
H(12) 0.3259 -0.4536 -0.3795 4.8
H(13) 0.4890 -0.6538 -0.2605 5.9
H(14) 0.4726 -0.4942 -0.2062 5.9
H(15) 0.3667 -0.4730 -0.0135 4.7

4.7

H(16)

0.3226

-0.5980

-0. 1017

Table A.15. continued

atom

H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)

X

-0.0322
0.0952
0.0990
0.2399
0.1334
0.2778
0.1724
0.0208

292

-0.3391
-0.4550
-0.4465
-0.5065
-0.2570
-0.3207
-0. 1337
-0.1089

0.21 10
0.1014
0.3606
0.2729
0.5040
0.4207
0.3469
0.3835

B(eq)

4.8
4.8
5.1
5.1
4.2
4.2
4.2
4.2

 

293

Table A.16. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
F62Cl4(2,2'-bpym)3 (3 4).

 

 

atom x y z B(eq)
Fe( 1) 0.08060(9) 0.50249(8) 0.30548(4) 1.82(2)
C1( 1) 0.3029(2) 0.3736(1) 0.21679(6) 2.1 1(4)
Cl(2) 0.3074(2) 0.8341(1) 0.37534(7) 247(4)
N(l) -0.0238(5) 0.6086(5) 0.1928(2) 2.0(1)
N(2) -0.2276(6) 0.4897(5) 0.0500(2) 2.6(1)
N(3) -0. 1882(5) 0.2478(5) 0.2356(2) 2.0(1)
N(4) -0.3739(6) 0.1 122(5) 0.0891(2) 2.6( 1)
N(5) 0.1361(5) 0.3808(5) 0.4246(2) 1.8(1)
N(6) 0.1278(5) 0.4381(5) 0.5871(2) 2.0(1)
C( 1) 0.0586(7) 0.7906(6) 0.1730(3) 2.3(1)
C(2) 0.0032(8) 0.8305(7) 0.0917(3) 2.8(2)
C(3) -0. 1410(8) 0.6734(7) 0.0323(3) 3 .0(2)
C(4) -0. 1623(6) 0.4654(6) 0.1299(3) 2.0(1)
C(5) -0.2491(6) 0.2629(6) 0.1522(3) 2.0(1)
C(6) -0.2707(7) 0.0691(7) 0.2576(3) 2.6(2)
C(7) -0.4039(7) -0.0960(7) 0.1973(3) 2.8(2)
C(8) -0.4486(7) -0.0666(7) 0.1 120(3) 2.8(2)
C(9) 0.2597(7) 0.2822(6) 0.4313(3) 2.2(1)
C(10) 0.3238(7) 0.2599(7) 0.5151(3) 2.5(2)
C(11) 0.2583(7) 0.3448(6) 0.5920(3) 2.3(1)
C(12) 0.0726(6) 0.4494(6) 0.5035(2) 1 .7(1)
H(1) -0. 175(7) 0.695(6) -0.029(3) 3 .2(9)
H(2) 0.055(7) 0.961(7) 0.079(3) 2.9(9)
H(3) 0.153(7) 0.894(6) 0.215(3) 2.6(8)
H(4) -0.526(7) -0. 180(7) 0.067(3) 2.6(8)
H(5) -0.464(6) -0.230(6) 0.216(3) 2.2(8)
H(6) -0.232(6) 0.065(6) 0.322(3) 25(8)
H(7) 0.302(6) 0.232(6) 0.371(3) 2.5(8)
H(8) 0.417(7) 0.192(6) 0.519(3) 3.1(9)
H(9) 0.3062 0.3377 0.6502 2.7

 

294

Table A.17. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
FeC12(2,2'-bpy) (36).

 

 

atom x y z B(eq)
Fe(l) 0 0.91441(7) 1/4 1.46(2)
Cl(1) -0.08499(4) 1.08621(9) -0.0087( 1) 1.69(3)
N ( 1) -0.0734( 1) 0.7247(3) 0.1022(4) 1.46(9)
C(l) -0.1511(2) 0.7312(4) -0.0363(5) 2.0(1)
C(2) -0. 1992(2) 0.6080(4) -0. 1059(5) 2.2( 1)
C(3) -0. 1663(2) 0.4720(4) -0.0349(5) 2.2(1)
C(4) -0.0870(2) 0.4630(4) 0.1037(5) 1 .8( 1)
C(5) -0.0424(2) 0.5904(3) 0.1725(4) 1 .5 (1)
H( 1) -0. 198(2) 0.379(4) -0.077(6) 3 .2(7)
H(2) -0.252(2) 0.617(4) —0.203(5) 2.4(7)
H(3) -0. 170(2) 0.827(4) -0.078(5) 1.8(7)
H(4) -0.065(2) 0.378(4) 0.160(5) 1.0(6)

 

295

Table A.18. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for

[Mn(2,2'-bpym)2(H20)2][BF4]2-20120).

 

 

atom x y z B(eq)
Mn(l) 0 ‘ 0.2057(2) 3/4 1.48(5)
0(1) 0.0478(2) 0.4173(5) 0.7328(3) 1.9(2)
N( 1) 0.0774(3) 0.0177(6) 0.7646(4) 1.6(2)
N(2) 0.2107(3) -0.0902(7) 0.8882(4) 1.8(2)
N(3) 0.1 134(3) 0.1705(6) 0.9273(4) 1.5(2)
N(4) 0.2464(3) 0.0619(7) 1.0512(4) 2.1(2)
C( 1) 0.0593(3) -0.0637(8) 0.6851(4) 2.1(2)
C(2) 0.1 140(3) -0. 1612(8) 0.7025(5) 2.3(3)
C(3) 0.1903(3) -0. 1689(8) 0.8062(5) 2.2(3)
C(4) 0.1531(3) -0.0023(7) 0.8636(5) 1.6(2)
C(5) 0.1713(3) 0.0830(8) 0.9519(4) 1.5(2)
C(6) 0.1316(3) 0.2468(7) 1.0085(5) 2.0(2)
C(7) 0.2063(3) 0.2345(9) 1.1117(5) 2.2(3)
C(8) 0.2618(3) 0.1408(9) 1.1292(5) 2.3(3)
0(2) 0.3801(2) 0.1392(5) 0.6072(3) 2.2(2)
F( 1) 0.3617(3) 0.0465(6) 0.3639(3) 5 .1(2)
F(2) 0.4632(2) 0.2280(6) 0.4349(3) 4.6(2)
F (3) 0.4502(2) 0.1289(5) 0.5364(3) 3.2(2)
F(4) 0.3634(3) 0.3236(6) 0.4035(4) 5 .7(2)
B(l) 0.4097(4) 0.184(1) 0.4335(6) 2.5(3)
H(1) 0.0065 -0.0534 0.6141 2.4
H(2) 0.1002 -0.2209 0.6457 2.8
H(3) 0.2298 -0.2335 0.8201 2.6
H(4) 0.0916 0.3108 0.9938 2.3
H(5) 0.2193 0.2890 1.1693 2.5
H(6) 0.3138 0.1307 1.2004 2.8
H(7) 0.0343 0.4536 0.6702 2.2

 

296

Table A.19. Atomic positional parameters and equivalent isotropic
displacement parameters (A2) and their estimated standard deviations for
[H-TMPP]2[C02C16] (3 9).

 

 

atom x y z B(eq)
Co(1) 0.52650(8) 0.1525(1) 051019(5) 1.93(5)
Cl(1) 0.4956(2) 0.0162(2) 0.4231(1) 2.3( 1)
Cl(2) 0.4094(2) 0.3021(2) 0.4968(1) 2.8(1)
Cl(3) 0.6782(2) 0.2284(3) 0.5355(1) 3 .9(1)
P(l) 0.9210(1) 0.0245(2) 0.2953(1) 1.44(9)
0(1) 1.0203(4) -0. 1407(5) 0.3862(2) 2.0(2)
0(2) 1.1821(4) -0.4080(6) 0.2662(3) 3 .0(3)
0(3) 0.9612(4) -0.0711(5) 0.1741(2) 2.0(2)
0(4) 0.7075(4) 0.0188(5) 0.2389(3) 2.1(2)
0(5) 0.6939(4) 0.3410(6) 0.0845(3) 2.7(3)
0(6) 1.0001(4) 0.1938(5) 0.2222(2) 1 .9(2)
0(7) 0.8275(4) 0.1976(6) 0.3538(2) 2.1(2)
0(8) 1.0964(4) 0.4404(6) 0.4768(3) 2 5(3)
0(9) 1.1392(4) 0.0826(6) 0.3445(2) 2.3(3)
C(1) 0.9949(6) -0. 1049(8) 0.2812(4) 1.5(3)
C(2) 1.0435(6) -0. 1796(8) 0.3337(4) 1.6(3)
C(3) 1.1070(6) -0.2810(8) 0.3322(4) 1.6(3)
C(4) 1.1220(6) -0.3120(8) 0.2750(4) 2.1(4)
C(5) 1.0731(6) -0.2443(8) 0.2205(4) 2.0(4)
C(6) 1.0117(5) -0. 1408(8) 0.2246(4) 1.7(3)
C(7) 0.8513(5) 0.1 104(7) 0.2286(4) 1 .3(2)
C(8) 0.7512(6) 0.1045(8) 0.2086(4) 1.8(4)
C(9) 0.6994(6) 0.1847(8) 0.1601(4) 2.0(4)
C( 10) 0.7505(6) 0.2677(8) 0.1312(4) 1.9(4)
C(1 1) 0.8527(6) 0.2729(8) 0.1490(4) 1.5(3)
C(12) 0.9013(6) 0.1942(8) 0.1982(4) 1.5(3)
C(13) 0.9829(5) 0.1424(8) 0.3513(3) 1.5(3)
C(14) 0.9249(5) 0.2251(8) 0.3755(4) 1.5(3)
C(15) 0.9637(6) 0.3242(8) 0.4175(4) 1.6(3)
C(16) 1.0642(6) 0.3408(8) 0.4356(4) 1.6(3)
C(17) 1.1258(5) 0.2601(8) 0.4135(4) 1.5(3)
C(18) 1.0847(6) 0.1626(8) 0.3710(4) 1.5(3)
C(19) 1.0556(6) 0.2155(9) 0.4420(4) 2.5(4)
C(20) 1.2306(7) -0.488(1) 0.3177(5) 4.4(5)
C(21) 0.9781(7) -0.096(1) 0.1 146(4) 2.8(4)
C(22) 0.6044(6) 0.028(1) 0.2279(4) 2.6(4)

C(23)

0.7392(7)

0.436(1)

0.0554(4)

3.1(4)

Table A.19. continued

atom

C(24)
C(25)
C(26)
C(27)
H(1)

H(2)

H(3)

H(4)

H(5)

H(6)

H(7)

H(8)

H(9)

H(10)
H(l 1)
H(12)
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
H(21)
H(22)
H(23)
H(24)
H(25)
H(26)
H(27)
H(28)
H(29)
H(30)
H(31)
H(32)
H(33)
H(34)

X

l 0606(6)
0.7585(6)
1 . 1996(6)
1 .2420(6)

0.8754
1.1394
1.0820
0.6301
0.8871
0.9226
1.1946
1.0343
1.0314
1.1250
1.1836
1 .2703
1.2703
0.9629
0.9380
1.0447
0.5880
0.5737
0.5834
0.7718
0.7850
0.6910
1.1271
1.0504
1.0443
0.7718
0.7634
0.6945
1.2301
1.2241
1 .2131
1.2602
1.2700
1 .2649

297

Y

0.262(1)
0.2787(9)
0.4608(9)
0.086(1)
-0.0224
-0.3279
-0.2690
0.1826
0.3281
0.3794
0.2714
-0.1761
-0.3029
-0.2172
-05321
-05507
-0.4340
-0. 1850
-0.0395
-0.0796
0.1 124
0.0133
-0.0373 .
0.4994
0.3944
0.4793
0.2513
0.2264
0.3526
0.2774
0.3665
0.2465
0.3836
0.4795
0.5326
0.0639
0.0247
0.1720

Z

0.1910(4)
0.3720(4)
0.4981(4)
0.3678(4)

0.3157
0.3687
0.1816
0.1470
0.1281
0.4335
0.4273
0.4744
0.4354
0.4534
0.3332
0.3048
0.3494
0.1031
0.0844
0.1 172
0.2395
0.1852
0.2519
0.0853
0.0381
0.0236
0.2135
0.1505
0.1881
0.4159
0.3585
0.3538
0.5184
0.4637
0.5262
0.4107
0.3458
0.3628

B(eq)

2.8(4)
2.7(4)
2.8(4)
2.6(4)

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