Description
Continuing a bestselling text’s legacy of presenting our current understanding of d block organometallic compounds, their reactivity, and use in synthesis
Fully updated to reflect recent advances, the 8th edition of The Organometallic Chemistry of the Transition Metals provides readers with a comprehensive introduction to the principles and general properties of organometallic compounds as well as practical information on reaction mechanisms and detailed descriptions of contemporary applications. Maintaining the style from prior editions, the author replaces older or dated citations with current ones and changes coverage of the subject to keep the material up to date.
The new edition emphasizes such growing topics as organic applications, nanoclusters, electro- and photo-catalysis, computational studies, radical pathways, spin state effects, molecular electronics, proton coupled electron transfer, and alternative energy applications. It also adds new X-ray techniques and computational aspects that can help students design more detailed experiments.
Sample topics covered in The Organometallic Chemistry of the Transition Metals include:
- Werner complexes, the trans effect, soft versus hard ligands and metals, the crystal and ligand fields, and choice of metals
- The 18 Electron Rule, bridging ligands, electron counting in reactions, Z ligands and the oxidation state concept and its limitations
- Structure, bonding, synthesis, and reactivity of metal carbenes
- Dissociative, associative, and photochemical substitution
- Mechanisms of oxidative addition and reductive elimination
A long-time bestseller, this new edition of The Organometallic Chemistry of the Transition Metals continues to be the leading textbook on the subject for advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry and practicing chemists in related fields.
Table of Contents
Preface xi
List of Abbreviations xiii
Periodic Table of the Elements xvii
1 Introduction 1
1.1 Why Study Organometallic Chemistry? 2
1.2 Coordination Chemistry 3
1.3 Werner Complexes 5
1.4 The Trans Effect 9
1.5 Soft Versus Hard Ligands and Metals 11
1.6 The Crystal Field 13
1.7 The Ligand Field 24
1.8 Two-Electron Three-Center Bonding 26
1.9 Back Bonding 26
1.10 Choice of Metals 30
1.11 The sd n Model and Hypervalent Bonding 32
References 37
Problems 39
2 Making Sense of Organometallics 41
2.1 Valence Electron Counting 41
2.2 The 18-Electron “Rule” 44
2.3 Electron Counting for Common Ligands 45
2.4 Bridging Ligands 49
2.5 Zero-Electron Ligands 51
2.6 Limitations of the 18-Electron Rule 54
2.7 Electron Counting in Reactions 57
2.8 The Oxidation State Concept and its Limitations 59
2.9 Coordination Number and Geometry 65
2.10 Effects of Complexation on Ligands 67
2.11 Differences between Metals 71
2.12 Ligand Types 76
2.13 Noninnocent Ligands and Ambiguous Oxidation States 83
References 85
Problems 87
3 Alkyls Aryls and Hydrides 89
3.1 Stability of Alkyls and Aryls 89
3.2 Making Alkyls and Aryls 98
3.3 Other σ-Bonded Ligands 106
3.4 Metal Hydrides 108
3.5 Sigma Complexes 111
3.6 Metal-Ligand Bond Strengths 115
References 118
Problems 121
4 Ligands and Substitution 123
4.1 Metal Carbonyls: Structure and Bonding 123
4.2 Metal Carbonyls: Synthesis and Reactivity 127
4.3 Bridging Carbonyls and CO Analogues 130
4.4 Nitrosyls 132
4.5 Phosphines and Related P-Donor Ligands 135
4.6 N-Heterocyclic Carbenes (NHC) 139
4.7 Dissociative Substitution 140
4.8 Associative Substitution 145
4.9 Redox Effects and Interchange Substitution 147
4.10 Photochemical Substitution 149
4.11 Other Factors in Substitution 152
4.12 Metal-Ligand Cooperativity 154
References 155
Problems 157
5 Pi-Complexes 159
5.1 Alkene and Alkyne Complexes 159
5.2 Allyl Complexes 166
5.3 Diene Complexes 170
5.4 Cyclopentadienyl Complexes 172
5.5 Arenes and Related Ligands 180
5.6 Metallacycles 183
5.7 Polyene Versus Polyenyl Complexes 184
5.8 Perfluorocarbon Ligands 184
References 185
Problems 186
6 Oxidative Addition and Reductive Elimination 189
6.1 General Principles 189
6.2 Concerted Additions 192
6.3 SN2 Pathways 195
6.4 Radical Mechanisms 197
6.5 Ionic Mechanisms 200
6.6 Reductive Elimination 202
6.7 Some Catalytic Applications of OA/RE Sequences 208
6.8 Sigma Bond Metathesis 212
6.9 Oxidative Coupling 213
6.10 Ligand-Assisted 12-Additions and Eliminations 214
References 215
Problems 216
7 Insertion and Elimination 219
7.1 Introduction 219
7.2 11-Insertion 221
7.3 12-Insertion 226
7.4 Outer Sphere Insertions 229
7.5 Beta Elimination and Related Processes 231
7.6 Alkene Isomerization Catalysis 233
7.7 Dehydrogenative Oxidation and Hydrogen Borrowing Catalysis 236
References 239
Problems 240
8 Addition and Abstraction 243
8.1 Types of Reaction 243
8.2 Nucleophilic Addition to CO 246
8.3 Nucleophilic Addition to Polyenes and Polyenyls 248
8.4 The Wacker Process 252
8.5 Nucleophilic Abstraction and Deprotonation 254
8.6 Electrophilic Addition and Abstraction 256
8.7 Electron Transfer and Radical Pathways 259
8.8 Proton-coupled Electron Transfer 260
References 263
Problems 264
9 Homogeneous Catalysis 267
9.1 Catalytic Cycles 268
9.2 Catalytic Hydrogenation 275
9.3 Alkene Hydroformylation 284
9.4 Alkene Hydrocyanation 286
9.5 Alkene Hydrosilylation 287
9.6 Cross-Coupling Reactions 288
9.7 Oxidation Catalysis 292
9.8 Electrocatalysis 294
9.9 Photoredox Catalysis 295
9.10 Catalyst Decomposition and Deactivation 298
References 299
Problems 303
10 Physical Methods 307
10.1 Mechanism 307
10.2 1Hand 2H NMR Spectroscopy 309
10.3 13C NMR Spectroscopy 315
10.4 31P NMR Spectroscopy 315
10.5 Dynamic NMR 318
10.6 Electron Paramagnetic Resonance Spectroscopy 320
10.7 IR Spectroscopy 323
10.8 Structure Determination 327
10.9 Electrochemistry 329
10.10 Computation 330
10.11 Big Data Artificial Intelligence and Machine Learning 331
10.12 Other Methods 332
References 334
Problems 337
11 Carbenes Carbynes and M–L Multiple Bonding 339
11.1 Carbenes 339
11.2 Carbynes 350
11.3 Bridging Carbenes and Carbynes 352
11.4 N-Heterocyclic Carbenes 353
11.5 Carbide and Carbone Complexes 357
11.6 Multiple Bonds to Heteroatoms 358
References 361
Problems 362
12 Metathesis Polymerization and Bond Activation 365
12.1 Alkene Metathesis 365
12.2 Alkene Dimerization Oligomerization and Polymerization 372
12.3 Activation of CO and CO2 380
12.4 C–H Activation and Functionalization 384
References 390
Problems 391
13 Green Energy & Materials Applications 395
13.1 Green Chemistry 395
13.2 Organometallics for an Alternative Energy Future 401
13.3 Metal–Metal Bonds and Clusters 404
13.4 Nanoparticles 407
13.5 Organometallic Materials 409
13.6 Supported Organometallics 415
References 417
Problems 420
14 Organic Applications 423
14.1 Carbon–Carbon and Carbon-heteroatom Coupling 424
14.2 C–H Activation and Late-stage Functionalization 431
14.3 Metathesis of C=C Bonds 436
14.4 Carbenes in Cyclopropanation and C–H Insertion 438
14.5 Hydrogenation 440
14.6 Oxidation 442
14.7 Carbonylation 444
14.8 Photoredox Catalysis 445
14.9 Alkyne and Aryne Chemistry 448
14.10 Radical Chemistry 450
14.11 Hydroboration 450
14.12 Electrosynthesis 451
14.13 Isotope Exchange 452
References 453
Problems 457
15 High Oxidation States Magnetism and the f-Block 461
15.1 High Oxidation States 461
15.2 Magnetism and Spin States 463
15.3 Cyclopentadienyl Complexes 472
15.4 The f-block 475
References 484
Problems 485
16 Bioorganometallic Chemistry 487
16.1 Introduction 488
16.2 Coenzyme B12 495
16.3 Iron-sulfur Clusters 501
16.4 Nitrogen Fixation 504
16.5 Nickel Enzymes 511
16.6 Applications to Chemical Biology 516
16.7 Biomedical and Biocatalytic Applications 517
References 521
Problems 524
Appendix A: Useful Texts on Allied Topics 527
Appendix B: Major Reaction Types 529
Answers 531
Index 549
