Robert H. Crabtree F.R.S. is Whitehead Professor of Chemistry at Yale, a Fellow of the Royal Society and of the American Chemical Society, and a member of the American Academy and of the National Academy of Sciences.

Preface xi
 
Acknowledgments xiii
 
List of Abbreviations xv
 
1 Introduction 1
 
1.1 Why Study Organometallic Chemistry? 1
 
1.2 Coordination Chemistry 3
 
1.3 Werner Complexes 3
 
1.4 The Trans Effect 7
 
1.5 Soft Versus Hard Ligands 9
 
1.6 The Crystal Field 10
 
1.7 The Ligand Field 17
 
1.8 Two-Electron Three-Center Bonding 19
 
1.9 Four-Electron Three-Center Bonding 20
 
1.10 Back Bonding 22
 
1.11 Trends in d Orbital Energies 26
 
1.12 Types of Ligand 27
 
References 32
 
Problems 33
 
2 Making Sense of Organometallics 35
 
2.1 The 18-Electron Rule 35
 
2.2 Limitations of the 18-Electron Rule 43
 
2.3 Electron Counting in Reactions 45
 
2.4 The Oxidation State Concept and its Limitations 46
 
2.5 Electroneutrality 52
 
2.6 Coordination Number and Geometry 53
 
2.7 Effects of Complexation 56
 
2.8 Differences between Metals 58
 
References 62
 
Problems 63
 
3 Alkyls and Hydrides 65
 
3.1 Alkyls and Aryls 65
 
3.2 Other sigma-Bonded Ligands 79
 
3.3 Metal Hydrides 80
 
3.4 Sigma Complexes 83
 
3.5 Bond Strengths 86
 
References 88
 
Problems 89
 
4 Ligand Substitution 91
 
4.1 Metal Carbonyls 91
 
4.2 Phosphines 100
 
4.3 N-Heterocyclic Carbenes 103
 
4.4 Dissociative Substitution 105
 
4.5 Associative Substitution 109
 
4.6 Redox Effects and Interchange Substitution 111
 
4.7 Photochemical Substitution 113
 
4.8 Counterions and Solvents in Substitution 115
 
References 116
 
Problems 118
 
5 Pi Complexes 121
 
5.1 Alkene and Alkyne Complexes 121
 
5.2 Allyl Complexes 126
 
5.3 Diene Complexes 130
 
5.4 Cyclopentadienyl Complexes 133
 
5.5 Arenes and Other Alicyclic Ligands 140
 
5.6 Metalacycles 143
 
5.7 Stability of Polyene and Polyenyl Complexes 144
 
References 145
 
Problems 145
 
6 Oxidative Addition and Reductive Elimination 147
 
6.1 Introduction 147
 
6.2 Concerted Additions 149
 
6.3 SN2 Pathways 152
 
6.4 Radical Mechanisms 153
 
6.5 Ionic Mechanisms 155
 
6.6 Reductive Elimination 156
 
6.7 Sigma Bond Metathesis 162
 
6.8 Ligand-Assisted 1,2-Additions and Eliminations 163
 
6.9 Oxidative Coupling 164
 
6.10 Proton-Coupled Electron Transfer 165
 
References 166
 
Problems 167
 
7 Insertion and Elimination 169
 
7.1 Introduction 169
 
7.2 1,1-Insertion 171
 
7.3 1,2-Insertion 175
 
7.4 Outer Sphere Insertions 179
 
7.5 alpha-,ß-,gamma- and delta-Elimination 180
 
References 182
 
Problems 182
 
8 Addition and Abstraction 185
 
8.1 Introduction 185
 
8.2 Nucleophilic Addition to CO 187
 
8.3 Nucleophilic Addition to Polyenes and Polyenyls 189
 
8.4 Nucleophilic Abstraction 196
 
8.5 Electrophilic Addition and Abstraction 197
 
8.6 Single-Electron Transfer and Radical Reactions 200
 
References 201
 
Problems 202
 
9 Homogeneous Catalysis 205
 
9.1 Catalytic Cycles 205
 
9.2 Alkene Isomerization 211
 
9.3 Hydrogenation 213
 
9.4 Alkene Hydroformylation 221
 
9.5 Alkene Hydrocyanation 223
 
9.6 Alkene Hydrosilylation 224
 
9.7 Coupling Reactions 225
 
9.8 Organometallic Oxidati

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Provides vital information on organometallic compounds, their preparation, and use in synthesis, and explores the fundamentals of the field and its modern applications
 
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