The Organometallic Chemistry of the Transition Metals, 5th Edition

List of Abbreviations xi

1 Introduction 1

1.1 Why Study Organometallic Chemistry?, 1

1.2 Coordination Chemistry, 2

1.3 Werner Complexes, 3

1.4 The Trans Effect, 7

1.5 Soft versus Hard Ligands, 8

1.6 The Crystal Field, 9

1.7 The Ligand Field, 16

1.8 Back Bonding, 19

1.9 Electroneutrality, 23

1.10 Types of Ligand, 25

2 General Properties of Organometallic Complexes 33

2.1 The 18-Electron Rule, 33

2.2 Limitations of the 18-Electron Rule, 39

2.3 Electron Counting in Reactions, 41

2.4 Oxidation State, 42

2.5 Coordination Number and Geometry, 46

2.6 Effects of Complexation, 49

2.7 Differences between Metals, 52

2.8 Supramolecular Chemistry, 54

3 Metal Alkyls, Aryls, and Hydrides and Related s-Bonded Ligands 58

3.1 Transition Metal Alkyls and Aryls, 58

3.2 Related s-Bonded Ligands, 73

3.3 Metal Hydride Complexes, 75

3.4 σ Complexes, 78

3.5 Bond Strengths for Classical σ-Bonding Ligands, 82

4 Carbonyls, Phosphine Complexes, and Ligand Substitution Reactions 88

4.1 Metal Complexes of CO, RNC, CS, and NO, 88

4.2 Phosphines and Related Ligands, 99

4.3 Dissociative Substitution, 104

4.4 Associative Substitution, 108

4.5 Redox Effects, The I Mechanism, and Rearrangements in Substitution, 111

4.6 Photochemical Substitution, 114

4.7 Steric and Solvent Effects in Substitution, 117

5 Complexes of p-Bound Ligands 122

5.1 Alkene and Alkyne Complexes, 122

5.2 Allyl Complexes, 128

5.3 Diene Complexes, 132

5.4 Cyclopentadienyl Complexes, 136

5.5 Arenes and Other Alicyclic Ligands, 143

5.6 Metalacycles and Isolobal Replacement, 148

5.7 Stability of Polyene and Polyenyl Complexes, 149

6 Oxidative Addition and Reductive Elimination 153

6.1 Concerted Additions, 156

6.2 SN2 Reactions, 158

6.3 Radical Mechanisms, 160

6.4 Ionic Mechanisms, 163

6.5 Reductive Elimination, 164

6.6 s-Bond Metathesis, 170

6.7 Oxidative Coupling and Reductive Fragmentation, 172

7 Insertion and Elimination 177

7.1 Reactions Involving CO, 179

7.2 Insertions Involving Alkenes, 185

7.3 Other Insertions, 191

7.4 a, b, g, and d Elimination, 192

8 Nucleophilic and Electrophilic Addition and Abstraction 199

8.1 Nucleophilic Addition to CO, 202

8.2 Nucleophilic Addition to Polyene and Polyenyl Ligands, 204

8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls, 212

8.4 Electrophilic Addition, 213

8.5 Electrophilic Abstraction of Alkyl Groups, 216

8.6 Single-Electron Transfer Pathways, 218

8.7 Reactions of Organic Free Radicals with Metal Complexes, 219

9 Homogeneous Catalysis 225

9.1 Alkene Isomerization, 229

9.2 Alkene Hydrogenation, 231

9.3 Alkene Hydroformylation, 244

9.4 Hydrocyanation of Butadiene, 247

9.5 Alkene Hydrosilylation and Hydroboration, 250

9.6 Coupling Reactions, 252

9.7 Organometallic “Oxidase” Reactions, 254

9.8 Surface and Supported Organometallic Catalysis, 255

10 Physical Methods in Organometallic Chemistry 263

10.1 Isolation, 263

10.2 1H NMR Spectroscopy, 264

10.3 13C NMR Spectroscopy, 268

10.4 31P NMR Spectroscopy, 270

10.5 Dynamic NMR, 272

10.6 Spin Saturation Transfer, 276

10.7 T1 and the Nuclear Overhauser Effect, 277

10.8 Isotopic Perturbation of Resonance, 280

10.9 IR Spectroscopy, 283

10.10 Crystallography, 286

10.11 Other Methods, 288

11 Metal-Ligand Multiple Bonds 296

11.1 Carbenes, 296

11.2 Carbynes, 311

11.3 Bridging Carbenes and Carbynes, 313

11.4 N-Heterocyclic Carbenes, 315

11.5 Multiple Bonds to Heteroatoms, 319

12 Applications of Organometallic Chemistry 327

12.1 Alkene Metathesis, 327

12.2 Dimerization, Oligomerization, and Polymerization of Alkenes, 334

12.3 Activation of CO and CO2, 343

12.4 C–H Activation, 348

12.5 Organometallic Materials and Polymers, 354

13 Clusters, Nanoparticles, Materials, and Surfaces 361

13.1 Cluster Structures, 362

13.2 Structures, 362

13.3 The Isolobal Analogy, 374

13.4 Nanoparticles, 378

13.5 Giant Molecules, 381

13.6 Organometallic Materials, 381

14 Applications to Organic Synthesis 388

14.1 Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond Formation, 389

14.2 Metathesis, 396

14.3 Rhodium Carbenes in Cyclopropanation and C-H Insertion, 397

14.4 Hydrogenation and Related Reactions, 399

14.5 Carbonylation, 401

14.6 Oxidation, 405

14.7 C–H Activation, 408

14.8 Click Chemistry, 412

14.9 Noncatalytic Reactions, 413

15 Paramagnetic, High-Oxidation-State, and High-Coordination-Number Complexes 421

15.1 Magnetism and Spin States, 422

15.2 Polyalkyls, 429

15.3 Polyhydrides, 434

15.4 Cyclopentadienyl Complexes, 437

15.5 f-Block Complexes, 439

16 Bioorganometallic Chemistry 448

16.1 Introduction, 448

16.2 Coenzyme B12, 454

16.3 Nitrogen Fixation, 460

16.4 Nickel Enzymes, 467

16.5 Biomedical Applications, 472

Useful Texts on Allied Topics 477

Major Reaction Types 479

Solutions to Problems 481

Index 496