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The Organometallic Chemistry of the Transition Metals, 6th Edition

ISBN: 978-1-118-13807-6
520 pages
April 2014
The Organometallic Chemistry of the Transition Metals, 6th Edition (1118138074) cover image

Description

Fully updated and expanded to reflect recent advances, the sixth edition of this bestselling text provides 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:

  • 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
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Table of Contents

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

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Author Information

Robert H. Crabtree, Ph. D., is Whitehead professor in the Department of Chemistry at Yale University. He has served on the editorial boards of Chemical Reviews, New Journal of Chemistry, Journal of Molecular Catalysis, and Organometallics and has received numerous awards for his research accomplishments including the Centenary Prize of the Royal Society of Chemistry (2014) and the Organometallic Chemistry Prize of the American Chemical Society (1993).
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Reviews

“Overall, this book is an insightful, detailed and, most importantly, up-to-date view of organometallic chemistry.”  (Applied Organometallic Chemistry, 14 November 2014)

 

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