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Özet
Özet
A comprehensive introduction to principles and practices
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 certain life science aspects, such as metalloenzymes involving organometallic intermediates.
Fully updated and expanded to reflect recent advances, this Third 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 sections covering:
* Coupling reactions
* C-F bond activation
* Giant molecules
* Paramagnetic organometallics
* Surface organometallic chemistry
Additionally, those sections covering metal alkyls, aryls, hydrides, metallocene polymerization, and related s-bonded ligands have been substantially revised and updated.
The Organometallic Chemistry of the Transition Metals, Third 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.
Author Notes
Robert H. Crabtree, Ph.D., is a professor in the Department of Chemistry at Yale University.
Reviews (1)
Choice Review
Each edition of this organometallics book by Crabtree (Yale Univ.) keeps getting better. Many sections have been rewritten and new materials included, such as coupling reactions, C-F bond activation, paramagnetic organometallics, and surface organometallic chemistry. A few new problems have been added to the problem sets, a highlight of the book. Solutions to the problems offer explanations that are very helpful to students. The best additions (compared to the 1st ed., 1988) are the subtitles within each section of each chapter, which makes the book useful as a resource. The introduction and chapter on general properties are well written and offer an excellent overview. Three chapters illustrate sigma-bonded and pi-bonded ligands and their reactions. Details of the major types of reaction mechanisms appear in the chapters on oxidative addition and reductive elimination, insertion and elimination, and nucleophilic/electrophilic addition and abstraction. There is a practical chapter on homogeneous catalysis and an especially good one on physical methods. The remaining chapters offer practical applications of organometallics to carbenes and polymerization, metal-metal bonds, organic synthesis, oxidation complexes, and bioorganometallic chemistry. Chapters are well illustrated with numerous references to the literature. Useful for undergraduate and graduate students. W. H. Hohman Marietta College
Table of Contents
| 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 A-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 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 |
