Organometallic Chemistry

by Spessard, Gary O.; Miessler, Gary L.

• ISBN13: 9780195330991
• ISBN10: 0195330994
• Edition: 2nd
• Format: Hardcover
• Copyright: 2009-10-26
• Publisher: Oxford University Press

Summary

Spessard and Miessler's Organometallic Chemistry, originally published by Prentice Hall in 1997, is widely acknowledged as the most appropriate text for undergraduates and beginning graduate students taking this course. It is a highly readable and approachable text that starts with the basicinorganic chemistry needed to understand this advanced topic. Unlike the primary competing book by Crabtree (Wiley), S/M places a strong emphasis on structure and bonding in the first several chapters, which lay the foundation for later discussion of reaction types and applications. Theorganization of material is much more accessible for students who have never seen organometallic chemistry before. In addition to being pitched at the right level for undergraduate students, S/M presents outstanding explanations of important core topics such as molecular orbitals and bonding andsupports these discussions with detailed illustrations and praised end of chapter problems. The second edition has been significantly revised and updated to include advancements over the last ten years in NMR, IR spectroscopy, nanotechnology and physical methods. The authors have significantly updated four chapters (9, 10, 11 and 12). Chapter 9 (catalysis) has been revised to cover theadvances in catalytic cycle research. Chapter 10 in the first edition, which covered carbene complexes, metathesis, and polymerization, has been divided into two chapters in view of the expanded research efforts that have occurred over the last ten years in these areas. Chapter 10 in the secondedition now focuses on carbene complexes, and Chapter 11 covers aspects of metathesis and polymerization reactions including an expanded discussion of Schrock and Grubbs metal carbene catalysts. Chapter 12 (Chapter 11, first edition) is a substantially-revised treatment of the applications oforganometallic chemistry to organic synthesis. This chapter offers an extensive discussion of asymmetric hydrogenation and oxidation methodology as well as a greatly revised treatment of Tsuji-Trost allylation, the Heck reaction, and palladium-catalyzed cross-coupling reactions. The latter topicincludes discussion of the Stille, Suzuki, Sonogashira, and Negishi cross-couplings, reactions that have had a profound impact on the synthesis of anti-tumor compounds and other potent pharmaceuticals. In addition, the authors have included more molecular model illustrations, and introduced more modern examples and medical/medicinal applications across the text. They have included 53% more in-chapter exercises and end-of-chapter problems (23% more exercises and 81% more EOCs). The second editionhas been extensively updated to include current literature (62% more references to the chemical literature).

Table of Contents

Figures	p. xi
Preface	p. xvii
An Overview of Organometallic Chemistry
Striking Difference	p. 1
Historical Background	p. 4
Fundamentals of Structure and Bonding	p. 13
Atomic Orbitals	p. 13
Molecular Orbitals	p. 21
Computational Organometallic Chemistry	p. 42
The 18-Electron Rule	p. 53
Counting Electrons	p. 53
Why 18 Electrons?	p. 60
Square Planar Complexes	p. 69
The Carbonyl Ligand	p. 75
Bonding	p. 75
Binary Carbonyl Complexes	p. 83
Oxygen-Bonded Carbonyls	p. 86
Ligands Similar to CO	p. 87
IR Spectra	p. 92
Main Group Parallels with Binary Carbonyl Complexes	p. 96
Pi Ligands	p. 103
Linear Pi Systems	p. 103
Cyclic ? Systems	p. 107
Nuclear Magnetic Resonance Spectra of Organometallic Compounds	p. 127
Other Important Ligands	p. 136
Complexes Containing M-C, M=C, and M=C Bonds	p. 136
Hydride and Dihydrogen Complexes	p. 152
Phosphines and Related Ligands	p. 155
Fullerene Ligands	p. 160
Mass Spectra	p. 165
Organometallic Reactions I: Reactions That Occur at the Metal	p. 176
Ligand Substitution	p. 178
Oxidative Addition	p. 202
Reductive Elimination	p. 226
Organometallic Reactions II: Reactions Involving Modification of Ligands	p. 244
Insertion and Deinsertion	p. 244
Nucleophilic Addition to the Ligand	p. 267
Nucleophilic Abstraction	p. 285
Electrophilic Reactions	p. 289
Homogeneous Catalysis: The Use of Transition Metal Complexes in Catalytic Cycles	p. 311
Fundamental Concepts of Homogeneous Catalysis	p. 312
The Hydroformylation Reaction	p. 322
The Wacker-Smidt Synthesis of Acetaldehyde	p. 340
Hydrogenation	p. 350
Carbonylation of Methanol	p. 361
Hydrocyanation	p. 367
Specialty Chemicals	p. 375
Transition Metal-Carbene and-Carbyne Complexes: Structure, Preparation, and Chemistry	p. 393
Structure of Metal Carbenes	p. 394
Synthesis of Metal Carbene Complexes	p. 407
Reactions of Metal-Carbene Complexes	p. 419
Metal-Carbyne Complexes	p. 439
sMetathesis and Polymerization Reactions	p. 456
¿ Bond Metathesis	p. 456
Alkyne Metathesis	p. 486
Ziegler-Natta and Related Polymerizations of Alkenes	p. 492
¿ Bond Metathesis	p. 507
Applications of Organometallic Chemistry to Organic Synthesis	p. 522
Enantioselective Functional Group Interconversions	p. 524
Carbon-Carbon Bond Formation via Nucleophilic Attack on an ¿3-¿ Ligand: The Tsuji-Trost Reaction	p. 555
Carbon-Carbon Bond Formation via Carbonyl and Alkene Insertion	p. 567
Carbon-Carbon Bond Formation via Transmetalation Reactions (Cross-Coupling Reactions)	p. 584
Carbon-Carbon Bond Formation through Cyclization Reactions	p. 613
Isolobal Groups and Cluster Compounds	p. 640
The Isolobal Analogy	p. 640
Cluster Compounds	p. 650
List of Abbreviations	p. A-1
Answers to Exercises	p. A-5
Index	p. I-1
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