The Organometallic Chemistry of the Transition Metals, 7th Edition

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

Fully updated and expanded to reflect recent advances, the new, seventh edition of this bestselling text presents students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. Increased focus is given to organic synthesis applications, nanoparticle science, and green chemistry. This edition features up-to-date examples of fundamental reaction steps and greater emphasis on key topics like oxidation catalysis, CH functionalization, nanoclusters and nanoparticles, and green chemistry. New coverage is added for computational chemistry, energy production, and biochemical aspects of organometallic chemistry.

The Organometallic Chemistry of the Transition Metals, Seventh Edition provides new/enhanced chapter coverage of ligand-assisted additions and eliminations; proton-coupled electron transfer; surface, supported, and cooperative catalysis; green, energy, and materials applications; and photoredox catalysis. It covers coordination chemistry; alkyls and hydrides; Pi-complexes; and oxidative addition and reductive elimination. The book also features sections on insertion and elimination; spectroscopy; metathesis polymerization and bond activation; and more.

• Provides an excellent foundation of the fundamentals of organometallic chemistry
• Includes end-of-chapter problems and their solutions
• Expands and includes up-to-date examples of fundamental reaction steps and focuses on important topics such as oxidation catalysis, CH functionalization, nanoparticles, and green chemistry
• Features all new coverage for computational chemistry, energy production, and biochemical aspects of organometallic chemistry

The Organometallic Chemistry of the Transition Metals, Seventh Edition is an insightful book that will appeal to all advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry, as well as any practicing chemist in those fields.

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 σ-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 S_N2 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 α-,β-,γ- and δ-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 Oxidation Catalysis 227

9.9 Electrocatalysis 229

9.10 Photoredox Catalysis 229

9.11 Surface Supported Single-Atom and Cooperative Catalysis 231

References 233

Problems 235

10 Physical Methods 239

10.1 Mechanism 239

10.2 ¹H NMR Spectroscopy 240

10.3 ¹³C NMR Spectroscopy 243

10.4 ³¹P NMR Spectroscopy 244

10.5 Dynamic NMR 246

10.6 Spin Saturation Transfer 249

10.7 T₁ and the Nuclear Overhauser Effect 250

10.8 IR Spectroscopy 254

10.9 Crystallography 256

10.10 Electrochemistry and EPR 257

10.11 Computation 259

10.12 Other Methods 260

References 262

Problems 263

11 M–L Multiple Bonds 265

11.1 Carbenes 265

11.2 Schrock Carbenes 272

11.3 Carbynes 276

11.4 Bridging Carbenes and Carbynes 278

11.5 N-Heterocyclic Carbenes 279

11.6 Multiple Bonds to Heteroatoms 282

References 285

Problems 286

12 Metathesis Polymerization and Bond Activation 289

12.1 Alkene Metathesis 289

12.2 Alkene Dimerization, Oligomerization, and Polymerization 295

12.3 Activation of CO and CO₂ 301

12.4 C−H Activation 305

12.5 Dehydrogenative Oxidation and Hydrogen Borrowing 309

References 311

Problems 313

13 Green Energy and Materials Applications 317

13.1 Green Chemistry 317

13.2 Energy Chemistry 320

13.3 Clusters and Nanoparticles 323

13.4 Organometallic Materials 325

References 332

Problems 334

14 Organic Applications 337

14.1 Carbon–Carbon and Carbon–Heteroatom Coupling 338

14.2 Metathesis 343

14.3 Cyclopropanation and C–H Insertion 345

14.4 Hydrogenation 346

14.5 Carbonylation 348

14.6 Oxidation 350

14.7 C–H Activation 352

14.8 Click Chemistry and Cycloaddition 355

14.9 Photoredox Catalysis 356

References 359

Problems 360

15 Paramagnetic and High-Oxidation-State Complexes 363

15.1 Magnetism and Spin States 364

15.2 Cyclopentadienyl Complexes 371

15.3 f-Block Complexes 373

References 380

Problems 381

16 Bioorganometallic Chemistry 383

16.1 Introduction 384

16.2 Coenzyme B₁₂ 388

16.3 Nitrogen Fixation 394

16.4 Nickel Enzymes 402

16.5 Artificial Enzymes 407

16.6 Biomedical and Biocatalytic Applications 407

References 410

Problems 412

Appendix A: Useful Texts on Allied Topics 415

Appendix B: Major Reaction Types 419

Solutions to Problems 421

Index 437

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