The Organometallic Chemistry of the Transition Metals / Edition 4

The Organometallic Chemistry of the Transition Metals / Edition 4

by Robert H. Crabtree
     
 

ISBN-10: 0471662569

ISBN-13: 9780471662563

Pub. Date: 05/13/2005

Publisher: Wiley

Fully updated and expanded to reflect recent advances, this Fifth Edition of the classic 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. With

Overview

Fully updated and expanded to reflect recent advances, this Fifth Edition of the classic 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. With increased focus on organic synthesis applications, nanoparticle science, and green chemistry, the Fifth Edition brings this vital resource up to date.

Product Details

ISBN-13:
9780471662563
Publisher:
Wiley
Publication date:
05/13/2005
Edition description:
REV
Pages:
560
Product dimensions:
6.46(w) x 9.37(h) x 1.27(d)

Table of Contents

Acknowledgment x

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 σ-Bonded Ligands 58

3.1 Transition Metal Alkyls and Aryls 58

3.2 Related σ-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 π-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 ReductiveElimination 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 σ-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 α, β, γ, and δ 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

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