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More About This Title The Organometallic Chemistry of the Transition Metals, Sixth Edition
English
This edition features:
- New sections on Multifunctional Ligands, Oxidation Catalysis, and Green Chemistry
- Expanded discussion on topics from the fifth edition: Supramolecular Chemistry, N-Heterocyclic Carbenes, Coupling Reactions, Organometallic Materials, Applications to Organic Synthesis, and Bioorganometallic Chemistry
- End-of-chapter problems and their solutions
English
English
Preface xi
List of Abbreviations xiii
1 Introduction 1
1.1 Why Study Organometallic Chemistry?, 1
1.2 Coordination Chemistry, 3
1.3 Werner Complexes, 4
1.4 The Trans Effect, 9
1.5 Soft versus Hard Ligands, 10
1.6 The Crystal Field, 11
1.7 The Ligand Field, 19
1.8 The sdn Model and Hypervalency, 21
1.9 Back Bonding, 23
1.10 Electroneutrality, 27
1.11 Types of Ligand, 29
References, 37
Problems, 38
2 Making Sense of Organometallic Complexes 40
2.1 The 18-Electron Rule, 40
2.2 Limitations of the 18-Electron Rule, 48
2.3 Electron Counting in Reactions, 50
2.4 Oxidation State, 51
2.5 Coordination Number and Geometry, 57
2.6 Effects of Complexation, 60
2.7 Differences between Metals, 63
References, 66
Problems, 67
3 Alkyls and Hydrides 69
3.1 Alkyls and Aryls, 69
3.2 Other σ-Bonded Ligands, 84
3.3 Metal Hydrides, 86
3.4 Sigma Complexes, 89
3.5 Bond Strengths, 92
References, 95
Problems, 96
4 Carbonyls, Phosphines, and Substitution 98
4.1 Metal Carbonyls, 98
4.2 Phosphines, 109
4.3 N-Heterocyclic Carbenes (NHCs), 113
4.4 Dissociative Substitution, 115
4.5 Associative Substitution, 120
4.6 Redox Effects and Interchange Substitution, 122
4.7 Photochemical Substitution, 124
4.8 Counterions and Solvents in Substitution, 127
References, 129
Problems, 131
5 Pi-Complexes 134
5.1 Alkene and Alkyne Complexes, 134
5.2 Allyls, 140
5.3 Diene Complexes, 144
5.4 Cyclopentadienyl Complexes, 147
5.5 Arenes and Other Alicyclic Ligands, 154
5.6 Isolobal Replacement and Metalacycles, 158
5.7 Stability of Polyene and Polyenyl Complexes, 159
References, 160
Problems, 161
6 Oxidative Addition and Reductive Elimination 163
6.1 Introduction, 163
6.2 Concerted Additions, 166
6.3 SN2 Pathways, 168
6.4 Radical Mechanisms, 170
6.5 Ionic Mechanisms, 172
6.6 Reductive Elimination, 173
6.7 σ-Bond Metathesis, 179
6.8 Oxidative Coupling and Reductive Fragmentation, 180
References, 182
Problems, 182
7 Insertion and Elimination 185
7.1 Introduction, 185
7.2 CO Insertion, 187
7.3 Alkene Insertion, 192
7.4 Outer Sphere Insertions, 197
7.5 α, β, γ, and δ Elimination, 198
References, 201
Problems, 201
8 Addition and Abstraction 204
8.1 Introduction, 204
8.2 Nucleophilic Addition to CO, 207
8.3 Nucleophilic Addition to Polyenes and Polyenyls, 208
8.4 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls, 215
8.5 Electrophilic Addition and Abstraction, 216
8.6 Single-Electron Transfer and Radical Reactions, 219
References, 221
Problems, 222
9 Homogeneous Catalysis 224
9.1 Catalytic Cycles, 224
9.2 Alkene Isomerization, 231
9.3 Hydrogenation, 233
9.4 Alkene Hydroformylation, 242
9.5 Alkene Hydrocyanation, 245
9.6 Alkene Hydrosilylation and Hydroboration, 246
9.7 Coupling Reactions, 248
9.8 Organometallic Oxidation Catalysis, 250
9.9 Surface, Supported, and Cooperative Catalysis, 251
References, 253
Problems, 256
10 Physical Methods 259
10.1 Isolation, 259
10.2 1H NMR Spectroscopy, 260
10.3 13C NMR Spectroscopy, 264
10.4 31P NMR Spectroscopy, 266
10.5 Dynamic NMR, 268
10.6 Spin Saturation Transfer, 271
10.7 T1 and the Nuclear Overhauser Effect, 272
10.8 IR Spectroscopy, 276
10.9 Crystallography, 279
10.10 Electrochemistry and EPR, 281
10.11 Computation, 283
10.12 Other Methods, 285
References, 287
Problems, 288
11 M–L Multiple Bonds 290
11.1 Carbenes, 290
11.2 Carbynes, 302
11.3 Bridging Carbenes and Carbynes, 305
11.4 N-Heterocyclic Carbenes, 306
11.5 Multiple Bonds to Heteroatoms, 310
References, 313
Problems, 315
12 Applications 317
12.1 Alkene Metathesis, 317
12.2 Dimerization, Oligomerization, and Polymerization of Alkenes, 324
12.3 Activation of CO and CO2, 332
12.4 C–H Activation, 336
12.5 Green Chemistry, 343
12.6 Energy Chemistry, 344
References, 347
Problems, 349
13 Clusters, Nanoparticles, Materials, and Surfaces 353
13.1 Cluster Structures, 354
13.2 The Isolobal Analogy, 364
13.3 Nanoparticles, 368
13.4 Organometallic Materials, 371
References, 379
Problems, 381
14 Organic Applications 383
14.1 Carbon–Carbon Coupling, 384
14.2 Metathesis, 391
14.3 Cyclopropanation and C–H Insertion, 393
14.4 Hydrogenation, 394
14.5 Carbonylation, 396
14.6 Oxidation, 399
14.7 C–H Activation, 401
14.8 Click Chemistry, 405
References, 406
Problems, 408
15 Paramagnetic and High Oxidation-State Complexes 411
15.1 Magnetism and Spin States, 413
15.2 Polyalkyls and Polyhydrides, 420
15.3 Cyclopentadienyl Complexes, 425
15.4 f-Block Complexes, 426
References, 433
Problems, 435
16 Bioorganometallic Chemistry 436
16.1 Introduction, 437
16.2 Coenzyme B12, 442
16.3 Nitrogen Fixation, 449
16.4 Nickel Enzymes, 457
16.5 Biomedical and Biocatalytic Applications, 463
References, 465
Problems, 467
Appendix A: Useful Texts on Allied Topics 469
Appendix B: Major Reaction Types and Hints on Problem Solving 472
Solutions to Problems 475
Index 493
English
“Overall, this book is an insightful, detailed and, most importantly, up-to-date view of organometallic chemistry.” (Applied Organometallic Chemistry, 14 November 2014)
