The Organometallic Chemistry of the Transition Metals

by Crabtree, Robert H.

• ISBN13: 9781118138076
• ISBN10: 1118138074
• Edition: 6th
• Format: Hardcover
• Copyright: 2014-04-21
• Publisher: Wiley

Summary

Widely regarded as the premier text in this field, the sixth edition of The Organometallic Chemistry of the Transition Metals continues to provide students and researchers in organic chemistry with vital information on organometallic compounds, their preparation, and use in synthesis. Exploring the fundamentals of the field and its modern applications, each chapter has been updated with relevant examples in the field, modern trends, and new applications.

Table of Contents

Acknowledgment

List of Abbreviations

1 Introduction

1.1 Why Study Organometallic Chemistry? 1.1

1.2 Coordination Chemistry 1.2

1.3 Werner Complexes 1.3

1.4 The Trans Effect 1.5

1.5 Soft versus Hard Ligands 1.5

1.6 The Crystal Field 1.6

1.7 The Ligand Field 1.10

1.8 the sdⁿ Model and Hypervalency 1.11

1.9 Back Bonding 1.12

1.10 Electroneutrality 1.14

1.11 Types of Ligand 1.15

2 Making Sense of Organometallic Complexes

2.1 The 18-Electron Rule 2.1

2.2 Limitations of the 18-Electron Rule 2.6

2.3 Electron Counting in Reactions 2.7

2.4 Oxidation State 2.8

2.5 Coordination Number and Geometry 1.12

2.6 Effects of Complexation 2.13

2.7 Differences between Metals 2.15

3 Alkyls and Hydrides

3.1 Alkyls and Aryls 3.1

3.2 Other s-Bonded Ligands 3.9

3.3 Metal Hydrides 3.10

3.4 S???????? Complexes 3.12

3.5 Bond Strengths 3.13

4 Carbonyls Phosphines and Substitution

4.1 Metal Carbonyls 4.1

4.2 Phosphines 4.2

4.3  N-Heterocyclic Carbenes (NHCs) 4.8

4.4 Dissociative Substitution 4.9

4.5 Associative Substitution 4. 11

4.6 Redox Effects and Interchange Substitution 4.13

4.7 Photochemical Substitution 4.14

4.8 Counterions and Solvents in Substitution 4.15

5 Complexes of p-Bound Ligands

5.1 Alkene and Alkyne Complexes 5.1

5.2 Allyls 5.4

5.3 Diene Complexes 5.5

5.4 Cyclopentadienyl Complexes 5.7

5.5 Arenes and Other Alicyclic Ligands 5.9

5.6 Isolobal Replacement and Metalacycles 5.11

5.7 Stability of Polyene and Polyenyl Complexes 5.12

6 Oxidative Addition and Reductive Elimination

6.1 Introduction 6.1

6.2 Concerted Additions 6.2

6.3 S_N2 Pathways 6.4

6.4 Radical Mechanisms 6.5

6.5 Ionic Mechanisms 6.5

6.6 Reductive Elimination 6.7

6.7 s-Bond Metathesis 6.10

6.8 Oxidative Coupling and Reductive Fragmentation  6.10

7 Insertion and Elimination

7.1 Introduction 7.1

7.2 CO Insertion 7.2

7.3 Alkene Insertion 7.4

7.4 Other Insertions 7.7

7.5 a, b, g, and d Elimination 7.7

8 Nucleophilic and Electrophilic Addition and Abstraction

8.1 Introduction 8.1

8.2 Nucleophilic Addition to CO 8.2

8.3 Nucleophilic Addition to Polyene and Polyenyls 8.3

8.4 Nucleophilic Abstraction in Hydrides Alkyls and Acyls 8.4

8.5 Electrophilic Addition and Abstraction 8.7

8.6 Single-Electron Transfer and Radical Reactions 8.8

9 Homogeneous Catalysis

9.1 Catalytic Cycles 9.1

9.2 Alkene Isomerization 9.5

9.3 Hydrogenation 9.5

9.4 Alkene Hydroformylation 9.10

9.5 Alkene Hydrocyanation  9.11

9.6 Alkene Hydrosilylation and Hydroboration  9.11

9.7 Coupling Reactions  9.12

9.8 Organometallic Oxidation Catalysis  9.13

9.9 Surface and Supported Organometallic Catalysis  9.14

10 Physical Methods

10.1 Isolation 10.1

10.2 ¹H NMR Spectroscopy  10.1

10.3 ¹³C NMR Spectroscopy  10.3

10.4 ³¹P NMR Spectroscopy  10.3

10.5 Dynamic NMR  10.4

10.6 Spin Saturation Transfer  10.6

10.7 T₁ and the Nuclear Overhauser Effect  10.6

10.8 IR Spectroscopy  10.8

10.9 Crystallography  10.9

10.10 Electrochemistry and EPR 10.11

10.11 Computation 10.12

10.12 Other Methods 10.13

11 M—L Multiple Bonds

11.1 Carbenes  11.1

11.2 Carbynes 11.7

11.3 Bridging Carbenes and Carbynes 11.8

11.4 N-Heterocyclic Carbenes  11.8

11.5 Multiple Bonds to Heteroatoms 11.10

12 Applications

12.1 Alkene Metathesis 12.1

12.2 Dimerization Oligomerization and Polymerization of Alkenes  12.4

12.3 Activation of CO and CO₂  12.7

12.4 C–H Activation  12.9

12.5 Green Chemistry 12.12

12.6 Energy Chemistry 12.13

13 Clusters Nanoparticles Materials and Surfaces

13.1 Cluster Structures  13.1

13.2 The Isolobal Analogy  13.6

13.3 Nanoparticles 13.8

13.4 Organometallic Materials 13.10

14 Organic Applications

14.1 Carbon–Carbon Coupling 14.2

14.2 Metathesis  14.4

14.3 Cyclopropanation and C–H Insertion  14.5

14.4 Hydrogenation 14.5

14.5 Carbonylation  14.6

14.6 Oxidation  14.6

14.7 C–H Activation  14.8

14.8 Click Chemistry  14.10

15 Paramagnetic and High-Oxidation-State Complexes

15.1 Magnetism and Spin States 15.2

15.2 Polyalkyls and Polyhydrides  15.5

15.3 Cyclopentadienyl Complexes 15.7

15.4 f-Block Complexes 15.8

16 Bioorganometallic Chemistry

16.1 Introduction 16.1

16.2 Coenzyme B₁₂ 16.5

16.3 Nitrogen Fixation 16.8

16.4 Nickel Enzymes 16.12

16.5 Biomedical and Biocatalytic Applications 16.15

Useful Texts on Allied Topics 000

Major Reaction Types 000

Solutions to Problems 000

Index