by
Eric James Derrah
B.Sc. (Honours), Mount Allison University, 2003 A Dissertation Submitted in Partial Fulfillment of the
Requirements for the Degree of DOCTOR OF PHILOSOPHY in the Department of Chemistry
© Eric James Derrah, 2009 University of Victoria
All rights reserved. This dissertation may not be reproduced in whole or in part, by photocopying or other means, without permission of the author.
Probing the Reactivity of Ruthenium Indenyl Complexes in P-C Bond Forming Reactions
by
Eric James Derrah
B.Sc. (Honours), Mount Allison University, 2003
Supervisory Committee
Dr. Lisa Rosenberg, Supervisor (Department of Chemistry)
Dr. J. Scott McIndoe, Departmental Member (Department of Chemistry)
Dr. David A. Harrington, Departmental Member (Department of Chemistry)
Dr. Reuven Gordon, Outside Member (Department of Electrical and Computer Engineering)
Supervisory Committee
Dr. Lisa Rosenberg, Supervisor (Department of Chemistry)
Dr. J. Scott McIndoe, Departmental Member (Department of Chemistry) Dr. David A. Harrington, Departmental Member (Department of Chemistry)
Dr. Dr. Reuven Gordon, Outside Member (Department of Electrical and Computer Engineering)
Abstract
Asymmetric hydrophosphination, the addition of a P-H bond across a C-C double bond, is an attractive potential route to chiral phosphines, which have important applications in many other types of asymmetric catalysis. However, a highly active and stereoselective catalyst for this reaction has yet to be identified. The ruthenium indenyl complex [RuCl(η5
-indenyl)(PPh3)2] (1) was investigated as a potential catalyst for
hydrophosphination through an exploration of the steps involved in this process: substrate coordination, P-H bond activation, and P-C bond formation.
Substitution of triphenylphosphine ligands at the metal centre of 1 by alkyl- and aryl-substituted secondary phosphines (PR2H: R = Cy (a), Pri (b), Et (c), Ph (d) or Tolp
(e)) gave predominantly the monosubstituted secondary phosphine complexes [RuCl(η5
-indenyl)(PR2H)(PPh3)] (3a-e). Hydride ([RuH(η5-indenyl)(PR2H)(PPh3)] (6a,d)) and
cationic nitrile ([Ru(η5
-indenyl)(NCR')(PR2H)(PPh3)][PF6] (7a,d: R' = CH=CH2; 8a-b,d:
R = CH3)) derivatives of 3 were prepared and in all cases the potentially reactive P-H
bond of the secondary phosphine ligand did not interfere with the chemical transformation.
Deprotonation of the P-H bond of the bulky dialkylphosphine-substituted chloro complexes 3a-b with KOBut gave five-coordinate, planar terminal phosphido complexes [Ru(η5
-indenyl)(PR2)(PPh3)] (10a-b) that contain a unique Ru-PR2 π-bond. The
analogous phosphido complexes 10d-e, containing less bulky aryl substituents at phosphorus, were found to be unstable at room temperature and were observed only by low temperature 31P{1H} NMR spectroscopy.
Phosphido complexes 10a-b were found to be highly P-basic, capable of deprotonating the C-H bond of acetonitrile (pKa = 24) to give the metallated acetonitrile
complex [Ru(CH2CN)(η5-indenyl)(PR2H)(PPh3)] (9a-b), and to be very P-nucleophilic,
reacting with iodomethane (MeI) to give a new P-C bond in [RuI(η5
-indenyl)(PCy2Me)(PPh3)] (17a). As might be expected, the addition of donor ligands to
low-coordinate 10a-b was found to disrupt the Ru-PR2 π-bond to give six-coordinate
terminal phosphido complexes [Ru(η5
-indenyl)(L)(PR2H)(PPh3)], with pyramidal,
instead of planar, geometry at phosphorus. These additions are irreversible in the case of CO (19a-b) or PCy2H (21a), while pyridine (23a-b) or NCPh (24a-b) adducts were
shown by 31P{1H} NMR spectroscopy to be in equilibrium with 10a-b and the uncoordinated ligand.
The addition of known substrates for transition metal-mediated hydrophosphination, phenylacetylene and acrylonitrile, to 10a-b resulted in a [2+2] cycloaddition of the unsaturated C-C bond at the Ru-PR2 π-bond to give metallacyclic
complexes [Ru(η5-indenyl)(κ2
-PhC=CHPR2)(PPh3)] (27a-b) and [Ru(η5-indenyl)(κ2
-NCCHCH2PR2)(PPh3)] (32a-b) respectively. Surprisingly the addition of simple
non-activated olefins (i.e. ethylene, 1-hexene, or norbornene), which were not previously known to be active substrates for this reaction, also gave [2+2] cycloaddition products. These cycloaddition reactions were found to be 100% regioselective, and are also stereoselective in the case of substituted alkenes (>96%). Experimental evidence suggests that these P-C bond forming reactions proceed via a concerted [2+2] cycloaddition pathway.
Table of Contents
Supervisory Committee ... ii
Abstract ... iii
Table of Contents ...v
List of Tables ... xvii
List of Figures ... xxvi
List of Abbreviations ... xl List of Number Compounds... xliii Acknowledgments... xlv Chapter 1: Overview 1.1 Introduction ... 1
1.2 Asymmetric P-C Bond Formation Through Transition Metal-Catalyzed Phosphination ... 4
1.3 Asymmetric P-C Bond Formation Through Metal-Catalyzed Hydrophosphination ... 6
1.3.1 Organolanthanide-Catalyzed Intramolecular Hydrophosphination ... 7
1.3.2 Transition Metal-Catalyzed Intermolecular Hydrophosphination ... 10
1.4 Project Goals and Rationale ... 16
1.4.1 Ruthenium Indenyl Complexes as Potential Catalysts for Transition Metal Mediated P-C Bond Formation ... 17
1.4.1.1 Ligand Substitution Reactions of [Ru(η5-indenyl)Cl(PPh3)2] and the Origin of the Indenyl Effect ... 18
1.4.2 Coordination Chemistry of Substrates Relevant to Transition Metal-Catalyzed Hydrophosphination ... 24
1.4.2.1 General Properties of Phosphine Ligands ... 25
1.4.2.2 General Properties of Nitrile Ligands ... 27
1.4.3 Formation of Terminal Phosphido Ligands as a Prerequisite for P-C Bond Formation ... 28
1.5 Scope of this Thesis ... 30
1.6 References ...32
Chapter 2: Ligand Substitution Reactions of [RuCl(η5 -indenyl)(PPh3)2] with Substrates Relevant to Hydrophosphination 2.1 Introduction ... 37
2.1.1 Transition Metal Complexes of Secondary Phosphines ... 37
2.1.2 Cationic Ruthenium Nitrile Complexes of 1 ... 40
2.2 Triphenylphosphine Ligand Substitution Reactions of Secondary Phosphines at [Ru(η5 -indenyl)Cl(PPh3)2]: Scope and Limitations ... 41
2.2.1 Synthesis and Characterization of Monosubstituted Secondary Phosphine Complex [RuCl(η5 -indenyl)(PR2H)(PPh3)] ... 41
2.2.2 Demonstrated Chloride Lability in the Synthesis and Characterization of Di- and Trisubstituted Secondary Phosphine Complexes 4 and 5. ... 46
2.3 Preparation of Hydride Analogues of Chloro Complexes 3a,d ... 50
2.3.1 Synthesis and Characterization of [RuH(η5 -indenyl)(HPR2)(PPh3)] (6a,d) ... 51
2.3.2 Electronic Effects on Hydride Formation and Evidence for an Electron Rich Metal Centre ... 53
2.3.3 Variable Indenyl Orientation in Complexes 3a-e and 6a,d: its Impact on the 1H/13C{1H} NMR Spectra ... 54
2.4 Cationic Nitrile Complexes of Secondary Phosphines ... 59
2.4.1 Synthesis and Characterization of Cationic Acrylonitrile Complexes, [Ru(η5 -indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') and [Ru(η5 -indenyl)(NCCH=CH2)(PR2H)(PPh3)][PF6] (7 a,d) ... 60
2.4.2 Synthesis and Characterization of Cationic Acetonitrile Complexes, [Ru(η5 -indenyl)(NCMe)(PR2H)(PPh3)][PF6] (8a-b,d) ... 66
2.5 Analysis of P-H Bond Strength in Coordinated Secondary Phosphine Complexes... 67
2.5.1 The Addition of d4-Methanol to Complexes [RuCl(η5 -indenyl)(PR2H)(PPh3)] (3a,d) and [Ru(η5 -indenyl)(NCMe)(PR2H)(PPh3)][PF6] (8a,d) ... 69
2.5.2 The Addition of d4-Methanol to Hydride complexes [RuH(η5 -indenyl)(PR2H)(PPh3)] (6a,d) ... 70
2.6 Conclusions ... 71
2.7 Experimental ... 74
2.7.1 General Comments ... 74
2.7.2 Preparation of Monosubstituted Secondary Phosphine Complexes 3a-f ... 75
2.7.2.1 Synthesis of [RuCl(η5 -indenyl)(PCy2H)(PPh3)] (3a) ... 75 2.7.2.2 Synthesis of [RuCl(η5 -indenyl)(PPri2H)(PPh3)] (3b) ... 76 2.7.2.3 Synthesis of [RuCl(η5 -indenyl)(PEt2H)(PPh3)] (3c) ... 77 2.7.2.4 Synthesis of [RuCl(η5 -indenyl)(PPh2H)(PPh3)] (3d) ... 78 2.7.2.5 Synthesis of [RuCl(η5 -indenyl)(PTolp2H)(PPh3)] (3e) ... 79
2.7.2.6 Attempted Synthesis of [RuCl(η5
-indenyl)(PBut2H)(PPh3)] (3f) ... 80
2.7.3 Preparation of Hydride Complexes 6a,d ... 80
2.7.3.1 Synthesis of [RuH(η5 -indenyl)(PCy2H)(PPh3)] (6a) ... 80
2.7.3.2 Synthesis of [RuH(η5 -indenyl)(PPh2H)(PPh3)] (6d) ... 81
2.7.4 Preparation of Cationic Nitrile Complexes ... 81
2.7.4.1 Synthesis of [Ru(η5-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 81
2.7.4.2 Synthesis of [Ru(η5-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6] (7a) ... 82
2.7.4.3 Synthesis of [Ru(η5-indenyl)(NCCH=CH2)(PPh2H)(PPh3)][PF6] (7d) ... 83
2.7.4.4 Synthesis of [Ru(η5-indenyl)(NCMe)(PCy2H)(PPh3)][PF6] (8a) ... 83
2.7.4.5 Synthesis of [Ru(η5-indenyl)(NCMe)(PPri2H)(PPh3)][PF6] (8b) ... 84
2.7.4.6 Synthesis of [Ru(η5-indenyl)(NCMe)(PPh2H)(PPh3)][PF6] (8d) ... 85
2.7.5 NMR Tube Reactions of 3a,d, 6a,d and 8a,d ... 85
2.7.5.1 General Procedure ... 85
2.7.5.2 Addition of d4-Methanol to 3a,d ... 86
2.7.5.3 Addition of d4-Methanol to 6a ... 86
2.7.5.4 Addition of d4-Methanol to 6d ... 87
2.7.5.5 Addition of d4-Methanol to 8a ... 87
2.7.5.6 Addition of d4-Methanol to 8d ... 87
2.7.6 1H and 13C{1H} NMR Data Tables for Compounds 3a-e, 6a,d, 7a,b,d, and 8a,d ... 88
2.8 References ... 94
Chapter 3: Coordinatively Unsaturated Ruthenium Phosphido Complexes Containing a Unique Ru-P π-Bond 3.1 Introduction ... 97
3.1.1 Spectroscopic Identification of Transition Metal Phosphido Complexes ... 97
3.1.2 P-H Bond Activation by Oxidative Addition of Secondary Phosphines ... 99
3.1.3 P-H Bond Activation by Deprotonation of Coordinated Secondary Phosphines ... 102
3.1.4 Coordinatively Unsaturated Ruthenium Half-Sandwich Complexes ... 103
3.1.4.1 Neutral, Operationally Unsaturated, Half-Sandwich Ruthenium Complexes of the General Formula [(C5R5)RuX(L)] ... 104
3.1.4.2 Cationic, Coordinatively Unsaturated, Half-Sandwich Ruthenium Complexes of the General Formula [(C5R5)Ru(L)2]+ ... 106
3.1.5 Strategy for Phosphido Formation from Ruthenium Indenyl Complexes 3,
6, and 8 ... 107
3.2 Attempted Deprotonation of the P-H Bond in Cationic Secondary Phosphine Complexes 8a,d: Unexpected Reactivity of Acetonitrile and Evidence for Phosphido Formation ... 110
3.3 Deprotonation of the P-H Bond in Neutral Secondary Phosphine Complexes 6a,d and 3a-b,d-e ... 114
3.3.1 Attempted Deprotonation of Hydride Complexes 6a,d ... 114
3.3.2 Deprotonation of Dialkylphosphine Chloro Complexes 3a-b Leading to a Coordinatively Unsaturated Half-Sandwich Compound [Ru(
η
5 -indenyl)(PR2)(PPh3)] (10a-b) ... 1153.3.2.1 DFT Calculations in Support of a Ru-P π-Bond in 10a... 120
3.3.2.2 Origin of the Unique Blue Colour of Complex 10a-b ... 123
3.3.3 Deprotonation of Aryl Chloride Complexes 3d-e: Evidence for the Formation of [Ru(η5 -indenyl)(PR2)(PPh3)] (10d-e) ... 125
3.4 Chemical Behavior in Solution of Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 127
3.4.1 Probing the Apparent Phosphido-Phosphaalkene Isomerization of 10a-b ... 128
3.4.2 Thermal Instability of Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) in Solution ... 137
3.5 Conclusions ... 139
3.6 Experimental ... 140
3.6.1 Preparation of [Ru(η5-indenyl)(NCCD3)(PCy2H)(PPh3)][PF6] (d3-8a) ... 141
3.6.2 Attempted Phosphido Formation from Cationic Complexes [Ru(η5 -indenyl)(NCMe)(PR2H)(PPh3)][PF6] (8a,d) ... 141
3.6.2.1 Preparation of [Ru(η5 -indenyl)(CH2CN)(PCy2H)(PPh3)] (9a) ... 141
3.6.2.2 Preparation of [Ru(η5 -indenyl)(CD2CN)(PCy2D)(PPh3)] (d3-9a) ... 142
3.6.2.3 Attempted Preparation of [Ru(η5 -indenyl)(CH2CN)(PPh2H)(PPh3)] (9d) ... 142
3.6.3 NMR Tube Reactions of [RuH(η5 -indenyl)(PR2H)(PPh3)] (6a,d) ... 142
3.6.4 Preparation of Coordinatively Unsaturated Phosphido Complexes 10a-b ... 143
3.6.4.1 Synthesis of [Ru(η5 -indenyl)(PCy2)(PPh3)] (10a) ... 143
3.6.4.2 Alternate, Large-Scale Prep of [Ru(η5 -indenyl)(PCy2)(PPh3)] (10a) ... 144
3.6.4.3 Synthesis of [Ru(η5 -indenyl)(PPri2)(PPh3)] (10b) ... 145
3.6.5 Low Temperature NMR experiments of [Ru(η5
-indenyl)(PR2)(PPh3)]
(10a-b) ... 145 3.6.6 EXSY NMR Experiments of 10b and 11b ... 146 3.6.7 Thermal Decomposition of [Ru(η5
-indenyl)(PCy2)(PPh3)] (10a) ... 147
3.6.8 Attempted Phosphido Formation from Aryl Substituted Secondary
Phosphine Complexes 3d-e ... 147 3.6.8.1 Addition of KOBut to 3d at Room Temperature ... 147 3.6.8.2 Monitoring the Formation of [Ru(η5
-indenyl)(PPh2)(PPh3)] (10d) from
3d at Low Temperatures ... 148 3.6.8.3 Addition of KOBut to 3e at Room Temperature ... 149 3.6.8.4 Monitoring the Formation of [Ru(η5
-indenyl)(PTolp2)(PPh3)] (10e)
from 3e at Low Temperatures ... 149 3.6.9 Computational Details ... 150 3.6.10 1H and 13C{1H} NMR Data Tables for Compounds 9a, 10a-d, 11a-d and
12a ... 151 3.7 References ...154 Chapter 4: Exploring the Nucleophilicity and Bronsted-Basicity of Terminal
Phosphido Complex [(η5-indenyl)Ru(PR2)(PPh3)] (10a-b)
4.1 Introduction ... 158 4.1.1 Unusual Behavior of Planar Phosphido Complexes ... 159 4.1.2 Oxidative Addition of Small Molecules at the Metal Centre of
Five-Coordinate Ruthenium Complexes ... 160 4.2 Establishing the Nucleophilic Character of Terminal Phosphido Complexes
[Ru(η5
-indenyl)(PR2)(PPh3)] (10a-b) Using Protic Reagents ... 161
4.2.1 Addition of Protic Reagents to [Ru(η5
-indenyl)(PCy2)(PPh3)] (10a) ... 161
4.2.2 Addition of Common Protic Solvents to 10a-b: Further Evidence of a
P-Basic Terminal Phosphido Ligand ... 165 4.2.1.1 Addition of Methanol to [Ru(η5
-indenyl)(PR2)(PPh3)] (10a-b): Further
Evidence of Phosphido/Phosphaalkene Isomerization ... 167 4.3 Reactivity of Phosphido Complexes [Ru(η5-indenyl)(PR2)(PPh3)] (10a-b)
toward Electrophilic Hydrocarbon Reagents ... 170 4.3.1 Addition of Iodomethane to Phosphido Complex 10a: Evidence of P-C
Bond Formation ... 171 4.3.2 Stability of Phosphido Complex 10a-b toward Common Halogenated
4.4 Apparent Heterolytic Addition of Non-Polar Substrates to the Ru-P π-Bond of Complex [Ru(η5 -indenyl)(PCy2)(PPh3)] (10a) ... 175 4.5 Conclusions ... 178 4.6 Experimental ... 179 4.6.1 General Synthesis ... 180 4.6.1.1 Preparation of [Ru(η5 -indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 180
4.6.1.2 Preparation of [RuI(η5 -indenyl)(PCy2Me)(PPh3)] (17a) ... 181
4.6.1.3 Preparation of [Ru(η5 -indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 181
4.6.2 NMR-Scale Reactions of [Ru(η5 -indenyl)(PCy2)(PPh3)] (10a) ... 182
4.6.2.1 Reaction with [HNEt3][Cl] ... 182
4.6.2.2 Reaction with HCl ... 182
4.6.2.3 Reaction with H2 ... 183
4.6.3 NMR Scale Reactions of 10a-b with Common Protic and Halogenated Organic Solvents ... 183 4.6.3.1 Addition of H2O ... 184 4.6.3.2 Addition of Methanol ... 184 4.6.3.3 Addition of ButOH ... 185 4.6.3.4 Addition of Dichloromethane ... 186 4.6.3.5 Addition of d1-Chloroform ... 186
4.6.4 1H and 13C{1H} NMR Data Tables for Isolated Compounds 13a•NH3, 17a and 18a ... 187
4.7 References ... 189
Chapter 5: Adduct-Induced Geometry Change at the Terminal Phosphido Ligand of [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) 5.1 Introduction ... 191
5.2 Coordination of Carbon Monoxide at Ruthenium in [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b,d-e) ... 196
5.2.1 Synthesis of Carbonyl Complexes [Ru(η5 -indenyl)(PR2)(CO)(PPh3)] (19a-b) ... 197
5.2.2 The Trapping of Aryl Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10d-e) with Carbon Monoxide ... 199
5.2.3 Solid State Structure of Carbonyl Complexes [Ru(η5 -indenyl)(PR2)(CO)(PPh3)] (19a,e) and Evidence in Support of the Gauche Effect ... 201
5.3 Preparation of Mixed Phosphido, Secondary Phosphine Complex [Ru(η5
-indenyl)(PCy2)(PCy2H)(PPh3)] (21a-b)... 205
5.4 Addition of O-Donor Solvents to Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 209
5.5 Addition of N-Donor Solvents to Phosphido Complexes [Ru(η5 -indenyl)(PPh2)(PPh3)] (10a-b) ... 211
5.5.1 Reversible Coordination of Pyridine to Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 211
5.5.1.1 Determination of Kinetic Parameters for the Reversible Coordination of Pyridine to Phosphido Complex 10a-b ... 213
5.5.1.2 Determination of Thermodynamic Parameters for the Reversible Coordination of Pyridine to Phosphido Complex 10a-b using the van’t Hoff Analysis. ... 216
5.5.2 Reversible Coordination of Benzonitrile to Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 217
5.5.2.1 Attempts to Determine Kinetic and Thermodynamic Parameters for the Reversible Coordination of Benzonitrile to Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 219
5.5.2.2 Increased Longevity of Terminal Phosphido Complexes 10a-b in the Presence of Benzonitrile ... 220
5.5.3 Metallation of Acetonitrile as More Evidence for the High Brønsted Basicity of Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) .... 221
5.5.3.1 Monitoring the Formation of [Ru(CH2CN)(η5-indenyl)(PR2H)(PPh3)] (9a-b) from [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) at Low Temperatures ... 226
5.5.3.1.1 Probing the Role of Acetonitrile Adduct [Ru(η5 -indenyl)(PR2)(NCMe)(PPh3)] (26a-b) in the Formation of [Ru(CH2CN)(η5-indenyl)(PR2H)(PPh3)] (9a-b) ... 228
5.5.3.1.2 Exploring the Formation of [Ru(CH2CN)(η5 -indenyl)(PCy2H)(PPh3)] (9a) from the Cationic Acetonitrile Complexes [Ru(η5 -indenyl)(NCMe)(PCy2H)(PPh3)][PF6] (8a): Support for an Intermolecular Pathway ... 233
5.6 Conclusion ... 234
5.7 Experimental ... 235
5.7.1 General Syntheses ... 236
5.7.1.1 Preparation of [Ru(η5 -indenyl)(PCy2)(CO)(PPh3)] (19a) ... 236
5.7.1.2 Preparation of [Ru(η5 -indenyl)(PPh2)(CO)(PPh3)] (19d) ... 237
5.7.1.4 Preparation of [Ru(η5
-indenyl)(PCy2)(PCy2H)(PPh3)] (21d) ... 239
5.7.1.5 Preparation of [Ru(CH2CN)(η5-indenyl)(PCy2H)(PPh3)] (9a) ... 239
5.7.1.6 Preparation of [Ru(CH2CN)(η5-indenyl)(PPri2H)(PPh3)] (9b) ... 240
5.7.2 NMR-Scale Reactions of [Ru(η5 -indenyl)(PR2)(PPh3)2] (10a-b) ... 241
5.7.2.1 Addition of Carbon Monoxide ... 241
5.7.2.2 Additions of diethyl ether and THF ... 242
5.7.2.3 Addition of Acetone Monitored at Low Temperatures ... 242
5.7.2.4 Addition of Pyridene Monitored at Low Temperatures ... 243
5.7.2.5 Addition of Benzonitrile Monitored at Low Temperatures ... 244
5.7.2.6 Addition of Acetonitrile Monitored at Room Temperature ... 245
5.7.2.7 Addition of Acetonitrile Monitored at Low Temperatures ... 246
5.7.2.8 Addition of 1:1 d0-Acetonitrile/d3-Acetonitrile at Room Temperatures... 246
5.7.3 Line-Shape Analysis of Low Temperature 31P{1H} NMR Spectra for the Reversible Coordination of Pyridine at the Ruthenium Centre of Complex 10a-b ... 247
5.7.4 van’t Hoff Analysis of Low Temperature 31P{1H} NMR Spectra for the Reversible Coordination of Pyridine at the Ruthenium Centre of Complex 10a-b ... 248
5.7.5 1H and 13C{1H} NMR Data Tables for all Isolated Compounds ... 250
5.8 References ... 254
Chapter 6: [2+2] Cycloaddition of Both Activated and Simple Alkynes and Alkenes at the Ru-P π-Bond of Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) 6.1 Introduction ... 257
6.1.1 [2+2] Cycloadditions of Unsaturated Substrates to the M-R2 Bond of Terminal Phosphido Complexes ... 257
6.1.2 [2+2] Cycloaddition Complexes as Intermediates in Catalytic Reactions Related to Transition Metal-Catalyzed Hydrophosphination ... 259
6.1.2.1 [2+2] Cycloadditions as the Key C-C Bond Forming Step in Olefin Metathesis ... 259
6.1.2.2 [2+2] Cycloadditions as the Key N-C Bond Forming Step in Transition Metal-Catalyzed Hydroamination ... 260
6.2 [2+2] Cycloaddition Reactions of Activated and Simple Alkynes at 10a-b ... 262
6.2.1 [2+2] Cycloaddition Reaction of Phenylacetylene at Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 262
6.2.1.1 Determination of Regiochemistry of the [2+2] Cycloaddition of Phenylacetylene to Phosphido Complexes [Ru(η5
-indenyl)(PR2)(PPh3)] (10a-b) ... 264
6.2.2 [2+2] Cycloaddition Reactions of Non-activated and Internal Alkynes at Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 268
6.3 [2+2] Cycloaddition Reaction of an Activated Michael-type Olefin at Phosphido Complexes [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 270
6.3.1 Synthesis and Characterization of [Ru(η5-indenyl)(κ2 -NCCHCH2PR2)(PPh3)] (32a-b) ... 270
6.3.1.1 Stereochemical Determination of syn-32 by NOESY NMR Spectroscopy and X-ray Crystallography ... 272
6.3.2 Rationale for the Preferred Formation of syn-[Ru(η5-indenyl)(κ2 -NCCHCH2PR2)(PPh3)] (syn-32a-b) ... 276
6.4 Unprecedented [2+2] Cycloaddition Reactions of Non-Activated, Simple Olefins at the Ru-P π-Bond in [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 278
6.4.1 Synthesis of [2+2] Cycloaddition Products [Ru(η5-indenyl)(κ2 -CHR'CHR'PR2)(PPh3)] 33a-b to 35a-b ... 278
6.4.2 Characterization of Cycloaddition product [Ru(η5-indenyl)(κ2 -CH2CH2PR2)(PPh3)] (33a-b) ... 280
6.4.3 Characterization and Stereochemical Determination of Cycloaddition Product syn-[Ru(η5-indenyl)(κ2 -BunCHCH2PR2)(PPh3)] (34a-b)... 281
6.4.4 Characterization and Stereochemical Determination of Cycloaddition Product [Ru(η5-indenyl)(κ2 -norborna-2,3-diyl-PR2)(PPh3)] (35a-b) ... 283
6.5 Mechanistic considerations for [2+2] cycloadditions of [Ru(η5 -indenyl)(PR2)(PPh3)] (10a-b) ... 289
6.5.1 Methods for Probing a Concerted [2+2] Cycloaddition Pathway ... 291
6.5.1.1 Complications Arising from the Addition of cis/trans-2-Butene to Phosphido Complexes 10a-b ... 294
6.5.1.2 Addition of trans-d2-Ethylene to [Ru(η5-indenyl)(PR2)(PPh3)] (10a-b) in Support of a Concerted [2+2] Cycloaddition Mechanism ... 297
6.5.2 Solvent Effects on the [2+2] Cycloaddition of 1-Hexene to 10a-b ... 301
6.6 Conclusion ... 303
6.7 Experimental ... 304
6.7.1 Preparation of Cycloaddition Products 27, and 32 – 35 ... 305
6.7.1.1 Synthesis of [Ru(η5-indenyl)(κ2 -PhC=CPhPCy2)(PPh3)] (27a) ... 305
6.7.1.2 Synthesis of [Ru(η5-indenyl)(κ2 -PhC=CPhPPri2)(PPh3)] (27b) ... 306
6.7.1.3 Synthesis of [Ru(η5-indenyl)(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 306
6.7.1.4 Synthesis of [Ru(η5-indenyl)(κ2 -NCCHCH2PPri2)(PPh3)] (32b) ... 307
6.7.1.5 Synthesis of [Ru(η5-indenyl)(κ2 -CH2CH2PCy2)(PPh3)] (33a) ... 307
6.7.1.7 Synthesis of [Ru(η5-indenyl)(κ2 -BunCH2CH2PCy2)(PPh3)] (34a) ... 308
6.7.1.8 Synthesis of [Ru(η5-indenyl)(κ2 -BunCH2CH2PPri2)(PPh3)] (34b) ... 309
6.7.1.9 Synthesis of [Ru(η5-indenyl)(κ2 -norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 309
6.7.1.10Synthesis of [Ru(η5-indenyl)(κ2 -norborna-2,3-diyl-PPri2)(PPh3)] (35b) .. 310
6.7.2 NMR Scale Reactions of 10a-b ... 310
6.7.2.1 Addition of Phenylacetylene to 10a-b ... 311
6.7.2.2 Addition of 1-Hexyne to 10a-b ... 311
6.7.2.3 Addition of Diphenylacetylene to 10a-b ... 312
6.7.2.4 Addition of Acrylonitrile to 10a-b ... 313
6.7.2.5 Addition of Ethylene to 10a-b ... 313
6.7.2.6 Addition of 1-Hexene to 10a-b ... 313
6.7.2.7 Addition of Norbornene to 10a-b ... 314
6.7.2.8 Addition of Cyclooctene to 10a-b ... 315
6.7.2.9 Addition of cis-2-Butene to 10a-b ... 315
6.7.2.10 Addition of trans-2-Butene to 10a-b ... 316
6.7.2.11 Addition of trans-d2-ethylene to 10a-b... 317
6.7.3 Monitoring the Rate of Addition of 1-Hexene to Phosphido Complexes 10a-b in Different Solvents. ... 317
6.7.4 Computational Details ... 319
6.7.5 1H, 13C{1H} and 31P{1H} NMR Data Tables for all Compounds ... 320
6.8 References ... 329
Chapter 7: Future Work 7.1 Introduction ... 332
7.2 Attempted Hydrophosphination of Phenylacetylene ... 333
7.2.1 Stoichiometric Ring-Opening Reactions of [Ru(η5-indenyl)(κ2 -PhC=CHPR2)(PPh3)] (27a-b) ... 334
7.3 Six-Coordinate Phosphido Complexes as Potential Catalysts for Hydrophosphination Reactions ... 337
7.4 Transition Metal-Mediated Phosphination ... 339
7.5.1 Attempted Hydrophosphination of Phenylacetylene Catalyzed by [Ru(η5
-indenyl)(PCy2)(PPh3)] (10a) ... 341
7.5.2 Addition of Phenylacetylene to [Ru(η5
-indenyl)(PCy2)(PCy2H)(PPh3)]
(21a) ... 341 7.6 References ... 342 Appendix A: X-Ray Crystallographic Structure Report for [Ru(η5
-
indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ...343 Appendix B: X-Ray Crystallographic Structure Report for [RuCl(η5-
indenyl)(PCy2H)(PPh3)] (3a) ...359 Appendix C: X-Ray Crystallographic Structure Report for [RuCl(η5
-
indenyl)(PPh2H)(PPh3)] (3d) ...372 Appendix D: X-Ray Crystallographic Structure Report for [RuCl(η5-
indenyl)(PTolp2H)(PPh3)] (3e) ...385 Appendix E: X-Ray Crystallographic Structure Report for [RuH(η5
-
indenyl)(PCy2H)(PPh3)] (6a) ...398 Appendix F: X-Ray Crystallographic Structure Report for [RuH(η5
-
indenyl)(PPh2H)(PPh3)] (6d) ...412 Appendix G: X-Ray Crystallographic Structure Report for [Ru(η5-
indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ...425 Appendix H: X-Ray Crystallographic Structure Report for [Ru(CH2CN)(η5
-
indenyl)(PCy2H)(PPh3)] (9d) ...440 Appendix I: X-Ray Crystallographic Structure Report for [Ru(η5-
indenyl)(PCy2)(PPh3)] (10d) ...453 Appendix J: X-Ray Crystallographic Structure Report for [Ru(η5
-
indenyl)(PPri2)(PPh3)] (10b) ...466 Appendix K: X-Ray Crystallographic Structure Report for [Ru(η5-
indenyl)(NH3)(PCy2H)(PPh3)][PF6](13a•NH3) ...477 Appendix L: X-Ray Crystallographic Structure Report for [Ru(η5
-
indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ...491 Appendix M: X-Ray Crystallographic Structure Report for [Ru(η5
-
indenyl)(PCy2)(CO)(PPh3)] (19a) ...506 Appendix N: X-Ray Crystallographic Structure Report for [Ru(η5-
indenyl)(PTolp2)(CO)(PPh3)] (19e) ...519 Appendix O: X-Ray Crystallographic Structure Report for [(η5-indenyl)Ru(κ
PhC=CHPCy2)(PPh3)] (27a) ...529 Appendix P: X-Ray Crystallographic Structure Report for [(η5-indenyl)Ru(κ2
- NCCHCH2PCy2)(PPh3)] (32a) ...543 Appendix Q: X-Ray Crystallographic Structure Report for [Ru(η5-indenyl)(κ2
- norborna-2,3-diyl-PCy2)(PPh3)] (35a) ...557
List of Tables
Table 1.1. Tolman cone angles (deg), and electronic factors (Xi) for selected
tertiary and secondary phosphines relevant to this project. ... 26 Table 2.1. Selected interatomic distances and bond angles for [RuCl(η5
-indenyl)(PR2H)(PPh3)] (3a,d,e). ... 44
Table 2.2. Selected interatomic distances and bond angles for [RuH(η5
-indenyl)(PR2H)(PPh3)] (6a,d). ... 52
Table 2.3. Selected interatomic distances and bond angles for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') and [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6] (7a). ... 66
Table 2.4. 500.13 MHz 1H NMR data for all complexes in d1-chloroform, except
6a,d in d6-benzene, at 300 K: δ in ppm (multiplicity, RI (relative integration),
Javg or ω1/2 in Hz). ... 88
Table 2.5 125.77 MHz 13C{1H} NMR data for all complexes in d1-chloroform,
except 6a,d in d6-benzene, at 300 K: δ in ppm (multiplicity, JPC or ω1/2 in Hz). ... 91
Table 3.1. Selected interatomic distances and bond angles for [Ru(η5
-indenyl)(PR2)(PPh3)] (10a-b). ... 119
Table 3.2. 500.13 MHz 1H NMR data for all complexes in d6-benzene at 300 K: δ
in ppm (multiplicity, RI, Javg or ω1/2 in Hz). ... 151
Table 3.3 125.77 MHz 13C{1H} NMR data for all complexes in d6-benzene, 300 K:
δ in ppm (multiplicity, JPC or ω1/2 in Hz).. ... 152
Table 4.1. 500.13 MHz 1H NMR data for all isolated complexes in d2
-dichloromethane for 13a•NH3 and d1-chloroform for 17a and 18a at 300 K: δ
in ppm (multiplicity, RI, Javg or ω1/2 in Hz). ... 187
Table 4.2 125.77 MHz 13C{1H} NMR data for all isolated complexes in d2
-dichloromethane for 13a•NH3 and d1-chloroform for 17a and 18a, at 300 K: δ
in ppm (multiplicity, JPC or ω1/2 in Hz). ... 188
Table 5.1. Selected interatomic distances and bond angles for [Ru(η5
-indenyl)(PR2)(CO)(PPh3)] (19a,e). ... 204
Table 5.2. Kinetic parameters determined for the equilibrium between phosphido
complexes 10a-b and pyridine adducts 23a-b. ... 215 Table 5.3. Thermodynamic parameters determined by the van’t Hoff analysis for
the equilibrium between phosphido complexes 10a-b and the pyridine adducts 23a-b. ... 217 Table 5.4. Line-shape analysis of VT-NMR spectra (31P{1H}) for the reversible
coordination of pyridine at the ruthenium centre of 10a. ... 248 Table 5.5. Line-shape analysis of VT-NMR spectra (31P{1H}) for the reversible
Table 5.6. van’t Hoff analysis of VT-NMR spectra (31P{1H} and 1H) for the
reversible coordination of pyridine at the ruthenium centre of 10a... 249 Table 5.7. van’t Hoff analysis of VT-NMR spectra (31P{1H} and 1H) for the
reversible coordination of pyridine at the ruthenium centre of 10b. ... 249 Table 5.8. 500.13 MHz 1H NMR data for all isolated complexes in d6-benzene at
300 K, except for 21a which was recorded at 360.13 MHz: δ in ppm
(multiplicity, RI, Javg or ω1/2 in Hz). ... 250
Table 5.9 125.77 MHz 13C{1H} NMR data for all isolated complexes in d6-benzene
at 300 K: δ in ppm (multiplicity, JPC or ω1/2 in Hz). ... 252
Table 6.1. Calculated second order rate constants (k) for the addition of 1-hexene to 10a-b with respect to changes in solvent polarity (Figure 6.26 and 6.27, see
Section 6.7.4). ... 303 Table 6.2. 500 MHz 1H NMR data for all major isomers at 300 K: δ in ppm
(multiplicity, RI, Javg or ω1/2 in Hz). ... 320
Table 6.3. 125 MHz 13C{1H} NMR data for all major isomers at 300 K: δ in ppm
(multiplicity, JPC or ω1/2 in Hz). ... 324
Table 6.4. 31P{1H} NMR data for all cycloaddition products at 300 K: δ in ppm
(multiplicity in Hz). ... 328 Table A.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 344
Table A.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 345
Table A.3. Selected Interatomic Distances (Å) for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 348
Table A.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 349
Table A.5. Torsional Angles (deg) for [Ru(η5-indenyl)(NCCH=CH2)(PPh3)2][PF6]
(2') ... 351 Table A.6. Least-Squares Planes for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6]
(2') ... 354 Table A.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 355
Table A.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') ... 357
Table B.1. Crystallographic Experimental Details for [RuCl(η5
Table B.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 361
Table B.3. Selected Interatomic Distances (Å) for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 363
Table B.4. Selected Interatomic Angles (deg) for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 364
Table B.5. Torsional Angles (deg) for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 365
Table B.6. Least-Squares Planes for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 368
Table B.7. Anisotropic Displacement Parameters (Uij, Å2) for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 369
Table B.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a) ... 370
Table C.1. Crystallographic Experimental Details for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 373
Table C.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 374
Table C.3. Selected Interatomic Distances (Å) for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 376
Table C.4. Selected Interatomic Angles (deg) for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 377
Table C.5. Torsional Angles (deg) for [RuCl(η5-indenyl)(PPh2H)(PPh3)] (3d) ... 378
Table C.6. Least-Squares Planes for [RuCl(η5-indenyl)(PPh2H)(PPh3)] (3d) ... 381
Table C.7. Anisotropic Displacement Parameters (Uij, Å2) for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 382
Table C.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d) ... 383
Table D.1. Crystallographic Experimental Details for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 386
Table D.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [RuCl(η5-indenyl)(PTolp2H)(PPh3)] (3e) ... 387
Table D.3. Selected Interatomic Distances (Å) for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 389
Table D.4. Selected Interatomic Angles (deg) for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 390
Table D.5. Torsional Angles (deg) for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 391 5
Table D.7. Anisotropic Displacement Parameters (Uij, Å2) for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 395
Table D.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e) ... 396
Table E.1. Crystallographic Experimental Details for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 399
Table E.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [RuH(η5-indenyl)(PCy2H)(PPh3)] (6a) ... 400
Table E.3. Selected Interatomic Distances (Å) for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 402
Table E.4. Selected Interatomic Angles (deg) for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 403
Table E.5. Torsional Angles (deg) for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 404
Table E.6. Least-Squares Planes for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 408
Table E.7. Anisotropic Displacement Parameters (Uij, Å2) for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 409
Table E.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) ... 410
Table F.1. Crystallographic Experimental Details for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 413
Table F.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 414
Table F.3. Selected Interatomic Distances (Å) for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 416
Table F.4. Selected Interatomic Angles (deg) for [RuH(η5
-indenyl)(PPh2H)(PPh3)]
(6d) ... 417 Table F.5. Torsional Angles (deg) for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 418
Table F.6. Least-Squares Planes for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 421
Table F.7. Anisotropic Displacement Parameters (Uij, Å2) for [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) ... 422
Table F.8. Derived Atomic Coordinates and Displacement Parameters for
Hydrogen Atoms for [RuH(η5-indenyl)(PPh2H)(PPh3)] (6d)... 423
Table G.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 426
Table G.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5
Table G.3. Selected Interatomic Distances (Å) for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 430
Table G.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 431
Table G.5. Torsional Angles (deg) for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 432
Table G.6. Least-Squares Planes for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 436
Table G.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) ... 437
Table G.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6](7a) .... 438
Table H.1. Crystallographic Experimental Details for [Ru(CH2CN)(η5
-indenyl)(PCy2H)(PPh3)] (9d) ... 441
Table H.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(CH2CN)(η5-indenyl)(PCy2H)(PPh3)] (9d)... 442
Table H.3. Selected Interatomic Distances (Å) for [Ru(CH2CN)(η5
-indenyl)(PCy2H)(PPh3)] (9d) ... 444
Table H.4. Selected Interatomic Angles (deg) for [Ru(CH2CN)(η5
-indenyl)(PCy2H)(PPh3)] (9d) ... 445
Table H.5. Torsional Angles (deg) for [Ru(CH2CN)(η5-indenyl)(PCy2H)(PPh3)]
(9d) ... 446 Table H.6. Least-Squares Planes for [Ru(CH2CN)(η5-indenyl)(PCy2H)(PPh3)]
(9d) ... 449 Table H.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(CH2CN)(η5
-indenyl)(PCy2H)(PPh3)] (9d) ... 450
Table H.8. Derived Atomic Coordinates and Displacement Parameters for
Hydrogen Atoms for [Ru(CH2CN)(η5-indenyl)(PCy2H)(PPh3)] (9d) ... 451
Table I.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(PCy2)(PPh3)] (10d). ... 454
Table I.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5
-indenyl)(PCy2)(PPh3)] (10d)... 455
Table I.3. Selected Interatomic Distances (Å) for [Ru(η5-indenyl)(PCy2)(PPh3)]
(10d) ... 457 Table I.4. Selected Interatomic Angles (deg) for [Ru(η5-indenyl)(PCy2)(PPh3)]
(10d) ... 458
Table I.6. Least-Squares Planes for [Ru(η5-indenyl)(PCy2)(PPh3)] (10d) ... 462
Table I.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(PCy2)(PPh3)] (10d) ... 463
Table I.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
-indenyl)(PCy2)(PPh3)] (10d) ... 464
Table J.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) ... 467
Table J.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5-indenyl)(PPri2)(PPh3)] (10b) ... 468
Table J.3. Selected Interatomic Distances (Å) for [Ru(η5-indenyl)(PPri2)(PPh3)]
(10b) ... 469 Table J.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(PPri2)(PPh3)]
(10b) ... 470 Table J.5. Torsional Angles (deg) for [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) ... 471
Table J.6. Least-Squares Planes for [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) ... 474
Table J.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) ... 475
Table J.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) ... 476
Table K.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 478 Table K.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters
for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 479 Table K.3. Selected Interatomic Distances (Å) for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 481
Table K.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 482
Table K.5. Torsional Angles (deg) for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6]
(13a•NH3) ... 483 Table K.6. Least-Squares Planes for [Ru(η5-indenyl)(NH3)(PCy2H)(PPh3)][PF6]
(13a•NH3) ... 487 Table K.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)][PF6] (13a•NH3) ... 488
Table K.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
Table L.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 492
Table L.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 493
Table L.3. Selected Interatomic Distances (Å) for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 495
Table L.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 496
Table L.5. Torsional Angles (deg) for [Ru(η5-indenyl)(SiEt3)(PCy2H)(PPh3)]
(18a) ... 497 Table L.6. Least-Squares Planes for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) .... 501
Table L.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 502
Table L.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)] (18a) ... 503
Table M.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 507
Table M.2. Atomic Coordinates and Equivalent Isotropic Displacement
Parameters for [Ru(η5-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 508
Table M.3. Selected Interatomic Distances (Å) for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 509
Table M.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 510
Table M.5. Torsional Angles (deg) for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 512
Table M.6. Least-Squares Planes for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 515
Table M.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 416
Table M.8. Derived Atomic Coordinates and Displacement Parameters for
Hydrogen Atoms for [Ru(η5-indenyl)(PCy2)(CO)(PPh3)] (19a) ... 517
Table N.1. Crystallographic Experimental Details for [Ru(η5
-indenyl)(PTolp2)(CO)(PPh3)] (19e) ... 520
Table N.2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2x 103) for [Ru(η5
-indenyl)(PTolp2)(CO)(PPh3)] (19e). U(eq) is
defined as one third of the trace of the orthogonalized Uij tensor. ... 522 Table N.3. Selected Interatomic Distances (Å) for [Ru(η5
Table N.4. Selected Interatomic Angles (deg) for [Ru(η5
-indenyl)(PTolp2)(CO)(PPh3)] (19e) ... 525
Table N.5. Anisotropic displacement parameters (Å2 x 103) for [Ru(η5 -indenyl)(PTolp2)(CO)(PPh3)] (19e). The anisotropicdisplacement factor
exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ... 526 Table N.6. Hydrogen coordinates (x 104) and isotropic displacement parameters
(Å2x 103) for [Ru(η5
-indenyl)(PTolp2)(CO)(PPh3)] (19e) ... 527
Table O.1. Crystallographic Experimental Details for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 530
Table O.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 531
Table O.3. Selected Interatomic Distances (Å) for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 533
Table O.4. Selected Interatomic Angles (deg) for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 534
Table O.5. Torsional Angles (deg) for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)]
(27a) ... 536 Table O.6. Least-Squares Planes for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)]
(27a) ... 539 Table O.7. Anisotropic Displacement Parameters (Uij, Å2) for [(η5
-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 540
Table O.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [(η5-indenyl)Ru(κ2
-PhC=CHPCy2)(PPh3)] (27a) ... 541
Table P.1. Crystallographic Experimental Details for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 544
Table P.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 545
Table P.3. Selected Interatomic Distances (Å) for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 547
Table P.4. Selected Interatomic Angles (deg) for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 548
Table P.5. Torsional Angles (deg) for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)]
(32a) ... 549 Table P.6. Least-Squares Planes for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)]
Table P.7. Anisotropic Displacement Parameters (Uij, Å2) for [(η5-indenyl)Ru(κ2 -NCCHCH2PCy2)(PPh3)] (32a) ... 553
Table P.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [(η5-indenyl)Ru(κ2
-NCCHCH2PCy2)(PPh3)] (32a) ... 555
Table Q.1. Crystallographic Experimental Details for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 558
Table Q.2. Atomic Coordinates and Equivalent Isotropic Displacement Parameters for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 559
Table Q.3. Selected Interatomic Distances (Å) for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 561
Table Q.4. Selected Interatomic Angles (deg) for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 562
Table Q.5. Torsional Angles (deg) for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 563
Table Q.6. Least-Squares Planes for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 567
Table Q.7. Anisotropic Displacement Parameters (Uij, Å2) for [Ru(η5 -indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)] (35a) ... 568
Table Q.8. Derived Atomic Coordinates and Displacement Parameters for Hydrogen Atoms for [Ru(η5-indenyl)(κ2
-norborna-2,3-diyl-PCy2)(PPh3)]
List of Figures
Figure 1.1. Chiral resolution of a phosphine oxide through the use of naturally
occurring menthol as a chiral ancillary in the synthesis of DiPAMP. ... 2 Figure 1.2. Proposed mechanism of Pd-catalyzed synthesis of (SP)-D from a
racemic mixture of P(Me)(Is)H. ... 5 Figure 1.3. Regioselectivity in organolanthanide-catalyzed intramolecular
hydrophosphination results from activation of both the nucleophile
(phosphine) and the electrophile (olefin). ... 9 Figure 1.4. Revised mechanism for Pt-catalyzed hydrophosphination proceeding
by nucleophilic attack on the electrophilic substrate. ... 12 Figure 1.5. Olefin activation pathway for [Ni(Pigiphos)(L)]2+-catalyzed
hydrophosphination of methylacrylonitrile by diadamantylphosphine. ... 15 Figure 1.6. Ruthenium catalyzed hydrophosphination of a terminal alkyne via
nucleophilic attack on a vinylidene intermediate... 16 Figure 1.7. η5-Indenyl complexes show some distortion towards an η3-coordination
mode, the driving force being the partial rearomatization of the benzene ring. ... 19 Figure 1.8. The five occupied frontier molecular orbitals for an indenyl ligand
available for coordination to a metal centre... 20 Figure 1.9. Common carbon and proton numbering scheme for indenyl ligands... 21 Figure 1.10. Indenyl effect: an associative mechanism for ligand substitution by a
phosphine proceeds via a “slipped” η3-indenyl intermediate. ... 22 Figure 1.11. Indenyl effect: a dissociative mechanism for phosphine substitution of
1 proceeding via an indenyl stabilized 16-electron intermediate (R) to give
monosubstituted complex S (L = PMePh2, PMe2Ph, PMe3)... 22
Figure 1.12. Bonding interactions between a phosphine ligand and a metal centre. ... 25 Figure 1.13. Definition of the Tolman cone angle for symmetric phosphines. ... 26 Figure 1.14. Nitrile ligands typically form adducts through the lone pair on
nitrogen (T) but coordination through the C-N triple bond (U) is known. Approximate IR νCN stretching frequencies for non-coordinated nitriles, N-bound (U) and side-on nitrile ligands (U) are listed below the corresponding
structures. ... 28 Figure 1.15. Common phosphido coordination modes in transition metal
complexes ... 29 Figure 2.1. 202.46 MHz 31P{1H} NMR (inset) and 500.13 MHz 1H NMR spectra
of [RuCl(η5
-indenyl)(PPri2H)(PPh3)] (3b) in d1-chloroform. Peaks in the 31
P{1H} NMR spectrum due to PPri2H and PPh3 are labeled accordingly and
impurities are marked with “§”. In the 1H NMR spectra peaks due to PPri2H
labeled as Ho, Hm, or Hp. Peaks due to the indenyl ligand in the 1H NMR
spectrum are labeled as per the diagram in the left hand corner and impurities
are marked with “§”. These spectra are typical of those observed for 3a-e. ... 43 Figure 2.2. Views of a) [RuCl(η5
-indenyl)(PCy2H)(PPh3)] (3a), b) [RuCl(η5
-indenyl)(PPh2H)(PPh3)] (3d), and c) [RuCl(η5-indenyl)(PTolp2H)(PPh3)] (3e)
showing the atom labeling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, hydrogen atoms attached to P1 and the indenyl ligand are shown with arbitrarily small thermal parameters; all other hydrogen atoms are not shown. (Structures a) and b) reproduced with permission from reference 3. Copyright 2005 American Chemical Society.) ... 45 Figure 2.3. Mechanism of hydride formation by β-hydride elimination from a
ruthenium methoxide intermediate. ... 50 Figure 2.4. Views of a) [RuH(η5
-indenyl)(PCy2H)(PPh3)] (6a) and b) [RuH(η5
-indenyl)(PPh2H)(PPh3)] (6d) showing the atom labeling scheme.
Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, all hydrogen atoms are shown with arbitrarily small thermal parameters except for the cyclohexyl and phenyl hydrogens which are not shown.
(Reproduced with permission from reference 3. Copyright 2005 American
Chemical Society.) ... 52 Figure 2.5. The aromatic region in the 500.13 MHz 1H NMR of compounds 3a-e
(spectra a – e respectively) in d1-chloroform at room temperature. The η5
-indenyl peaks are marked with * and ‡ indicates half of the P-H peak (3d-e),
which overlaps with an aromatic peak in the case of 3e. ... 55 Figure 2.6. Aromatic region of variable temperature (a) 125.77 MHz 13C{1H} and
(b) 500.13 MHz 1H NMR of coupound 3a in CDCl3. Where the η5-indenyl
peaks are marked with * and the aromatic peaks are labled with i (ipso), o (ortho), m (meta), and p (para). (Reproduced with permission from reference
3. Copyright 2005 American Chemical Society.) ... 55 Figure 2.7. a) Top view of complexes 3a,d showing the preferred orientation of the
indenyl ligand and b) side view showing the resulting interaction between the
ortho-proton of one aryl substituent on the PPh3 ligand and the six-membered
ring of the indenyl ligand. ... 57 Figure 2.8. The aromatic region in the 500.13 MHz 1H NMR of compounds 6a (a)
and 6d (b) in d6-benzene at room temperature, showing improved resolution of
peaks due to PPh3, relative to 3a,d. The η5-indenyl peaks are marked with “*”
and “●” indicates the residual solvent peak (C6D5H). ... 58
Figure 2.9. Top view of complexes 6a,d, demonstrating the preferred orientation of the indenyl ligand. ... 58 Figure 2.10. Top view of [RuCl(η5
-indenyl)(PTolp2H)(PPh3)] (3e), demonstrating
Figure 2.11. Partial 500.13 MHz 1H NMR spectrum of [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6] (7a) in d1-chloroform. Peaks due
to acrylonitrile and indenyl ligand are labeled according to the diagram in the right hand corner, peaks due to the PPh3 ligand are labeled as Ho, Hm, and Hp,
and the P-H peak of the secondary phosphine is labeled accordingly. ... 62 Figure 2.12. View of [Ru(η5
-indenyl)(NCCH=CH2)(PPh3)2][PF6] (2') showing the
atom labeling. The PF6- counterion has been removed for clarity.
Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, the hydrogen atoms attached to P1 and acrylonitrile are shown with
arbitrarily small thermal parameters; all other hydrogen atoms are not shown. ... 63 Figure 2.13. a) View of [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6] (7a)
showing the dominant orientation of the vinyl group and the atom labeling scheme. b) View of [Ru(η5
-indenyl)(NCCH=CH2)(PCy2H)(PPh3)][PF6] (7a)
showing both A and B orientations of the vinyl group. For clarity, the PF6
-counterion has been removed in both structures and the cyclohexyl and phenyl substituents are not shown in structure b. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, the hydrogen atoms attached to P1 and acrylonitrile are shown with arbitrarily small thermal
parameters; all other hydrogen atoms are not shown... 64 Figure 3.1. Bonding modes observed for terminal phosphido ligands. ... 97 Figure 3.2. General mechanism for the oxidative addition of the P-H bond of a
secondary phosphine ligand. ... 99 Figure 3.3. Calculated pyramidalization angle (α) as a measure of planarity at the
metal centre of coordinatively unsaturated half-sandwich complexes. ... 104 Figure 3.4. Donation of π-electrons from the X-type ligand stabilizes the
16-electron coordinatively unsaturated complex resulting in an “operationally”
unsaturated 18-electron configuration. ... 105 Figure 3.5. Potential products resulting from the addition of KOBut to d3-8a. ... 112
Figure 3.6. a) 55.28 MHz 2H NMR spectrum of crude d3-9a in benzene. (A peak
due to an unknown deuterium containing impurity is marked with “φ”.) b) 360.13 MHz 1H NMR spectrum of crude d3-9a in d6-benzene. (Peaks due to
unknown impurities are marked with “•”. Reproduced with permission from the supporting information accompanying reference 61. Copyright 2008
American Chemical Society.) ... 113 Figure 3.7. The 202.46 MHz 31P{1H} NMR spectra of 10a (a) and 10b (b) in d6
-benzene demonstrating the extreme downfield chemical shift resulting from the deprotonation of the P-H bond. Peaks due to 10a-b are marked with “•”,
11a-b is marked with “*”, and an unknown impurity with “‡”. ... 117 Figure 3.8. a) View of [Ru(η5
-indenyl)(PCy2)(PPh3)] (10a) and b) [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) showing the atom labeling schemes.
level, hydrogen atoms are not shown. (Structure of 10a reproduced with
permission from reference 5. Copyright 2007 American Chemical Society.) ... 119 Figure 3.9. Other known compounds exhibiting a Ru-P π-bond (Mes* =
2,4,6-tri-tert-butylphenyl). ... 120
Figure 3.10. Kohn-Sham frontier molecular orbitals of [Ru(η5
-indenyl)(PCy2)(PPh3)] (10a) calculated using DFT (hybrid PBE1PBE).
(Reproduced with permission from reference 5. Copyright 2007 American
Chemical Society.) ... 121 Figure 3.11. Occupied molecular orbitals of the Ru-P bonds in complex 10a
resulting from an NBO analysis: a) Ru-PPh3 σ; b) Ru-PCy2 σ; c) Ru-PCy2 π.
(Reproduced with permission from reference 5. Copyright 2007 American
Chemical Society.) ... 122 Figure 3.12. The effects of solvent polarity on ligand to metal charge transfer
(LMCT) process. ... 124 Figure 3.13. 145.80 MHz 31P{1H} NMR spectra demonstrating the formation of
phosphido complexes 10d (a) at 250K and 10e (b) at 260 K in d8-toluene.
Peaks due to 10d-e are marked with “•”, peaks due to unreacted 3d with “*”,
and all other peaks are unidentified decomposition products. ... 126 Figure 3.14. Alkyl region of the 500 MHz 1H (a) and 1H{31P} (b) NMR spectra of
a 84:16 mixture of 10b and 11b in d6-benzene. Peaks due to 10b are marked
with “•”, 11b are marked with “*”, and a pentane impurity is marked with “‡”. .. 130 Figure 3.15. Partial 500 MHz 1H-EXSY NMR spectrum of a mixture of 10b and
11b in d8-toluene, where peaks due to 10b are marked with “•”, peaks due to
11b are marked with “*”, and peaks due to a pentane impurity is marked with “‡”. Ovals indicate regions of the spectra where correlations between 10b and 11b were predicted to be observed. ... 134 Figure 3.16. Partial 500 MHz 1H-EXSY NMR spectrum of a mixture of 10b and
11b in d8-toluene with the addition of 2,6-lutidine, where peaks due to 10b are
marked with “•”, peaks due to 11b are marked with “*”, and peaks due to a
pentane impurity are marked with “‡”. ... 135 Figure 3.17. Proposed proton transfer mechanism for 2,6-lutidine assisted
phosphido (10a-b), phosphaalkene (11b) isomerization. ... 137 Figure 4.1. General reaction pathways available for terminal phosphido complexes. .. 158 Figure 4.2. View of the cation complex [Ru(η5
-indenyl)(NH3)(PCy2H)(PPh3)]+
(13a•NH3), showing the atom labeling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, while the hydrogen atoms attached to P(1) and N are shown with arbitrarily small thermal parameters; other hydrogen atoms are not shown. C* denotes the centroid of the plane defined by C(7a)-C(1)-C(2)-C(3)-C(3a), and ∆ (indenyl slip distortion) d[Ru-C(7a),C(3a)] - d[Ru-C(1),C(3)]. Selected interatomic
2.2717(5), Ru-N = 2.1896(17), Ru-C* = 1.905, P(1)-H(1P) = 1.30(2), ∆ = 0.13; P(1)-Ru-P(2) = 91.531(18), P(1)-Ru-N = 89.60(5), P(2)-Ru-N = 92.13(5), C*-Ru-P(1) = 127.2, C*-Ru-P(2) = 124.6, C*-Ru-N = 121.6. (Reproduced with permission from reference 15. Copyright 2007 American
Chemical Society.) ... 164 Figure 4.3. Variable temperature 145.78 MHz 31P{1H} NMR spectra of [Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) and methanol in d8-toluene. Peaks due to the
phosphaalkene isomer [RuH(η5
-indenyl)(P=C(CH3)2)(Pri)(PPh3)] (11b) are
marked with “†”, peaks due to methoxide intermediate [Ru(η5
-indenyl)(OMe)(PPri2H)(PPh3)] (15b) with “*”, and peaks due to [RuH(η5
-indenyl)(PPri2H)(PPh3)] (6b) with “•”. Peaks due to phosphido complex
[Ru(η5
-indenyl)(PPri2)(PPh3)] (10b) at 288.3 and 63.2 ppm were not observed
at any temperature. ... 169 Figure 4.4. Proposed equilibrium between phosphido complex 10a-b and the
phosphaalkene isomer 11a-b as observed from the addition of methanol to
10a-b in variable temperature 31P{1H} NMR experiments. ... 170 Figure 4.5. View of [Ru(η5
-indenyl)(SiEt3)(PCy2H)(PPh3)](18a), showing the
atom labeling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, while the hydrogen atom attached to P(1) is shown with arbitrarily small thermal parameters; other hydrogen atoms are not shown. C* denotes the centroid of the plane defined by C(7a)-C(1)-C(2)-C(3)-C(3a), and ∆ (indenyl slip distortion) C(7a),C(3a)] - d[Ru-C(1),C(3)]. Selected interatomic distances (Å) and bond angles (deg): Ru-P(1) = 2.2790(7), Ru-P(2) = 2.2802(7), Ru-Si = 2.4108(8), Ru-C* = 1.965, P(1)-H(1P) = 1.32(3), ∆ = 0.20; P(1)-Ru-P(2) = 96.05(3), P(1)-Ru-Si = 86.27(2), P2-Ru-Si = 96.19(2), C*-Ru-P(1) = 127.9, C*-Ru-P(2) = 125.0, C*-Ru-Si = 115.5. (Reproduced with permission from reference 15. Copyright 2007
American Chemical Society.) ... 177 Figure 5.1. a) Molecules that have lone pairs (hydrazine) or polar bonds
(1,2-difluoroethane) will prefer a gauche arrangement over the sterically favored
anti-periplanar conformation, a phenomenon known as the gauche effect, b)
due to electron delocalization by hyperconjugation. ... 195 Figure 5.2. A d-type orbital (AN) aligned with the Re-PPh3 bond of
[CpRe(NO)(PPh2)(PPh3)] (AM) directs the phosphido ligand to adopt a
conformation in the solid state where its lone pair is gauche to the Re-PPh3
bond: this is called the gauche effect. ... 195 Figure 5.3. Carbonyl ligands can donate electrons to the metal centre from the
HOMO orbital while accepting electron density from the metal centre into its
π* LUMO orbital. ... 196 Figure 5.4. 202.46 MHz 31P{1H} NMR spectrum of [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) in d6-benzene demonstrating the upfield
chemical shift of the phosphido ligand and small 2JPP coupling constant due to
Figure 5.5. 202.46 MHz 31P{1H} NMR spectrum of a) [Ru(η5
-indenyl)(PPh2)(CO)(PPh3)] (19d) and b) [Ru(η5-indenyl)(PTolp2)(CO)(PPh3)]
(19e) in d6-benzene demonstrating the upfield chemical shift of the phosphido
ligand and small 2JPP coupling constant due to the presence of a Ru-PR2 single
bond. ... 200 Figure 5.6. Views of a) [Ru(η5
-indenyl)(PCy2)(CO)(PPh3)] (19a) and b) [Ru(η5
-indenyl)(PTolp2)(CO)(PPh3)] (19e) showing the atom labeling schemes.
Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20% probability level, hydrogen atoms are not shown. (Structure of 19a reproduced with
permission from reference 30. Copyright 2007 American Chemical Society.) ... 203 Figure 5.7. Interactions between the lone pair on the phosphido ligand and a d-type
orbital along the Ru-PPh3 bond (AO) may result in the observed gauche
orientation of the phosphido ligand relative to the Ru-PPh3 in the molecular
structure of [Ru(η5
-indenyl)(PR2)(CO)(PPh3)] (19a,e). ... 205
Figure 5.8. 145.78 MHz 31P{1H} NMR spectrum of crude [Ru(η5
-indenyl)(PCy2)(PCy2H)(PPh3)] (21a) in d6-benzene. Peaks due to unknown
impurities are marked with “§” and all other peaks are labeled accordingly. ... 207 Figure 5.9. 145.78 MHz 31P{1H} NMR spectra (VT, d8-toluene) of the reaction of
10a with excess pyridine. Peaks due to phosphido complex 10a are marked with “•”, the phosphaalkene isomer 12a with “*”, the pyridine adduct 23a with “†” and an unknown impurity with “φ”. (Reproduced with permission from reference 31 (supporting information). Copyright 2008 American
Chemical Society.) ... 213 Figure 5.10. Sample a) simulated and b) experimental 145.78 MHz 31P{1H} NMR
spectra of the reaction of 10a with excess pyridine in d8-toluene at 250K.
Peaks due to 10a are marked with “•”, the phosphaalkene isomer 11a with “*”, the pyridine adduct 23a with “†”, and an unknown impurity is marked with “φ”. (Reproduced with permission from reference 31 (supporting
information). Copyright 2008 American Chemical Society.) ... 214 Figure 5.11. 145.78 MHz 31P{1H} NMR spectra in d8-toluene showing the change
in concentration of the coordinatively unsaturated phosphido complex 10b and the benzonitrile adduct 24b with increasing temperature. Peaks due to 10b are marked with “•”, the phosphaalkene isomer 11b with “*”, 24b with “†”, and peaks due to the amido impurity 25b are marked with “‡”. (Reproduced with permission from reference 31 (supporting information). Copyright 2008
American Chemical Society.) ... 219 Figure 5.12. The equilibrium between 10a-b and the benzonitrile adduct 24a-b,
strongly favors the adduct, leading to less decomposition of 10a-b by the
ortho-metallation pathway. ... 221
Figure 5.13. Alkyl and P-H region of the 500.13 Mz 1H and 1H{31P} spectra of 9a in d6-benzene. Peaks due to the P-H bond and metallated acetonitrile are