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The Organometallic Chemistry of the Transition Metals, 4th Edition

The Organometallic Chemistry of the Transition Metals, 4th Edition

Robert H. Crabtree

ISBN: 978-0-471-71875-8

Jun 2005

600 pages

Select type: E-Book



Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with an excellent 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.

List of Abbreviations.

1 Introduction.

1.1 Werner Complexes.

1.2 The Trans Effect.

1.3 Soft Versus Hard Ligands.

1.4 The Crystal Field.

1.5 The Ligand Field.

1.6 Back Bonding.

1.7 Electroneutrality.

1.8 Types of Ligand.

2 General Properties of Organometallic Complexes.

2.1 The 18-Electron Rule.

2.2 Limitations of the 18-Electron Rule.

2.3 Electron Counting in Reactions.

2.4 Oxidation State.

2.5 Coordination Number and Geometry.

2.6 Effects of Complexation.

2.7 Differences between Metals.

2.8 Outer-Sphere Coordination.

3 Metal Alkyls, Aryls, and Hydrides and Related σ-Bonded Ligands.

3.1 Transition Metal Alkyls and Aryls.

3.2 Related σ-Bonded Ligands.

3.3 Metal Hydride Complexes.

3.4 σ Complexes.

3.5 Bond Strengths for Classical σ-Bonding Ligands.

4 Carbonyls, Phosphine Complexes, and Ligand Substitution Reactions.

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

4.2 Phosphines and Related Ligands.

4.3 Dissociative Substitution.

4.4 Associative Mechanism.

4.5 Redox Effects, the I Mechanism, and Rearrangements in Substitution.

4.6 Photochemical Substitution.

4.7 Steric and Solvent Effects in Substitution.

5 Complexes of π-Bound Ligands.

5.1 Alkene and Alkyne Complexes.

5.2 Allyl Complexes.

5.3 Diene Complexes.

5.4 Cyclopentadienyl Complexes.

5.5 Arenes and Other Alicyclic Ligands.

5.6 Metalacycles and Isoelectronic and Isolobal Replacement.

5.7 Stability of Polyene and Polyenyl Complexes.

6 Oxidative Addition and Reductive Elimination.

6.1 Concerted Additions.

6.2 SN2 Reactions.

6.3 Radical Mechanisms.

6.4 Ionic Mechanisms.

6.5 Reductive Elimination.

6.6 σ-Bond Metathesis.

6.7 Oxidative Coupling and Reductive Cleavage.

7 Insertion and Elimination.

7.1 Reactions Involving CO.

7.2 Insertions Involving Alkenes.

7.3 Other Insertions.

7.4 α, β, γ, and δ Elimination.

8 Nucleophilic and Electrophilic Addition and Abstraction.

8.1 Nucleophilic Addition to CO.

8.2 Nucleophilic Addition to Polyene and Polyenyl Ligands.

8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls.

8.4 Electrophilic Addition.

8.5 Electrophilic Abstraction of Alkyl Groups.

8.6 Single-Electron Transfer Pathways.

8.7 Reactions of Organic Free Radicals with Metal Complexes.

9 Homogeneous Catalysis.

9.1 Alkene Isomerization.

9.2 Alkene Hydrogenation.

9.3 Alkene Hydroformylation.

9.4 Hydrocyanation of Butadiene.

9.5 Alkene Hydrosilation and Hydroboration.

9.6 Coupling Reactions.

9.7 Surface and Supported Organometallic Catalysis.

10 Physical Methods in Organometallic Chemistry.

10.1 Isolation.

10.2 1H NMR Spectroscopy.

10.3 13C NMR Spectroscopy.

10.4 31P NMR Spectroscopy.

10.5 Dynamic NMR.

10.6 Spin Saturation Transfer.

10.7 T1 and the Nuclear Overhauser Effect.

10.8 Isotopic Perturbation of Resonance.

10.9 IR Spectroscopy.

10.10 Crystallography.

10.11 Other Methods.

11 Metal–Ligand Multiple Bonds.

11.1 Carbenes.

11.2 Carbynes.

11.3 Bridging Carbenes and Carbynes.

11.4 N-Heterocyclic Carbenes.

11.5 Multiple Bonds to Heteroatoms.

12 Applications of Organometallic Chemistry.

12.1 Alkene Metathesis.

12.2 Dimerization, Oligomerization, and Polymerization of Alkenes.

12.3 Activation of CO and CO2.

12.4 CH Activation.

12.5 Organometallic Materials and Polymers.

13 Clusters and the Metal–Metal Bond.

13.1 Structures.

13.2 The Isolobal Analogy.

13.3 Synthesis.

13.4 Reactions.

13.5 Giant Clusters and Nanoparticles.

13.6 Giant Molecules.

14 Applications to Organic Synthesis.

14.1 Metal Alkyls Aryls, and Hydrides.

14.2 Reduction, Oxidation, and Control of Stereochemistry.

14.3 Protection and Deprotection.

14.4 Reductive Elimination and Coupling Reactions.

14.5 Insertion Reactions.

14.6 Nucleophilic Attack on a Ligand.

14.7 Heterocycles.

14.8 More Complex Molecules.

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

15.1 Magnetism and Spin States.

15.2 Polyalkyls.

15.3 Polyhydrides.

15.4 Cyclopentadienyl Complexes.

15.5 f -Block Complexes.

16 Bioorganometallic Chemistry.

16.1 Introduction.

16.2 Coenzyme B12.

16.3 Nitrogen Fixation.

16.4 Nickel Enzymes.

16.5 Biomedical Applications.

Useful Texts on Allied Topics.

Major Reaction Types.

Solutions to Problems.


" impressive and compressive book...this review would have to be book size to do full justice to all the insights in this volume." (Journal of Metals Online, May 23, 3006)