The Organometallic Chemistry of the Transition Metals

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.

Auteur
ROBERT H. CRABTREE, PhD, is a 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 Organometallic Chemistry Prize of Royal Society of Chemistry (1991) and the Organometallic Chemistry Prize of the American Chemical Society (1993).

Texte du rabat
"Each edition of this organometallics book . . . keeps getting better . . . useful as a reference . . . useful for undergraduate and graduate students."
—Choice on the Thir d Edition There have been a number of notable advances in the field of organometallic chemistry over the past decade. Transition metal organometallic chemistry has provided researchers– especially those working in the pharmaceuticals, natural product synthesis, and polymer industries–with powerful new synthetic tools, and the field has expanded to include life science aspects, such as metalloenzymes involving organometallic intermediates and nanotechnology, such as nanoparticles and giant molecules.

Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds. It also supplies a wealth of practical information about relevant reaction mechanisms, along with detailed descriptions of contemporary applications to organic synthesis, organized by reaction type. Additionally, the numerous references to pertinent literature found throughout the text are appreciated by students and professional chemists alike.

New to this edition are:

• A new section on elements of the f-block and expanded coverage of paramagnetic organometallic compounds.
• Extensively revisions to the chapter on organic synthetic applications including new sections on coupling, metathesis, nucleophilic substitution, Lewis acid reactions, chiral bases and other catalytic reactions
• Significant updates to the chapter on bioorganometallic chemistry, including hydrogenase, acetyl CoA synthase, and methyl CoM reductase, as well as a discussion of biomedical applications.
• Bibiliographic references to many useful reviews
  The Organometallic Chemistry of the Transition Metals, Fourth Edition is an unparalleled pedagogic resource, appropriate as a main text for courses in inorganic chemistry and organometallic chemistry, and as a supplementary text for courses in bioinorganic chemistry. It is also a valuable working reference for professional chemists who need to become better acquainted with the subject.

Contenu
Preface. 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 -Bonded Ligands.

3.1 Transition Metal Alkyls and Aryls.

3.2 Related -Bonded Ligands.

3.3 Metal Hydride Complexes.

3.4 Complexes.

3.5 Bond Strengths for Classical -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 -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 -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 , , , and 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 *T*1 and the Nuclear Overhauser Effect.

10.8 Isotopic Perturbation of Resonance.

10.9 IR Spectroscopy.

10.10 Crystallography.

10.11 Other Methods.

11 MetalLigand Multiple Bonds.

11.1 Carbenes.

11.2 Carbynes. 11.3 Bridging Carbenes and Carbynes.&l...