Organometallic Chemistry

Organometallic Chemistry


Author:
Gary O. Spessard & Gary L. Miessler
Published in: OXFORD UNIVERSITY PRESS
Release Year: 2010
ISBN: 978-0-19-533099-1
Pages: 732
Edition: Second Edition
File Size: 8 MB
File Type: pdf
Language: English



Description of Organometallic Chemistry

Organometallic chemistry is an exciting and rapidly expanding field that has changed considerably over the 12 years intervening between the first edition of our textbook and the appearance of this new edition. Since 1997, six organometallic chemists have been honored as Nobel Laureates because their work has had such an enormous impact, not only on the field but also to related areas of the chemical sciences, especially organic synthesis. The first edition indicated that π-bond metathesis would have a significant bearing on the course of organometallic chemistry. We now realize that the applications of metathesis to organic synthesis constitute one of the most significant advances in the ability to construct complex molecules to occur in the past 50 years. The ready availability of user-friendly software and high-speed computers has made computational chemistry and molecular modeling important and routinely used tools for the elucidation of organometallic reaction mechanisms. High-level molecular orbital calculations have helped unravel the mysteries of catalytic cycles and allowed chemists to develop new chemistry based on the results and predictions of these computations. Recent developments in organometallic chemistry have been highly beneficial to practitioners of materials science, who produce exciting new substances, often through organotransition metal-catalyzed polymerization reactions.

Content of Organometallic Chemistry

Chapter 1 An Overview of Organometallic Chemistry 1
1-1 Striking Difference 1
1-2 Historical Background 4
Chapter 2 Fundamentals of Structure and Bonding 13
2-1 Atomic Orbitals 13
2-2 Molecular Orbitals 21
2-3 Computational Organometallic Chemistry 42
Chapter 3 The 18-Electron Rule 53
3-1 Counting Electrons 53
3-2 Why 18 Electrons? 60
3-3 Square Planar Complexes 69
Chapter 4 The Carbonyl Ligand 75
4-1 Bonding 75
4-2 Binary Carbonyl Complexes 83
4-3 Oxygen-Bonded Carbonyls 86
4-4 Ligands Similar to CO 87
4-5 IR Spectra 92
4-6 Main Group Parallels with Binary
Carbonyl Complexes 96
Chapter 5 Pi Ligands 103
5-1 Linear Pi Systems 103
5-2 Cyclic π Systems 107
5-3 Nuclear Magnetic Resonance Spectra of
Organometallic Compounds 127

Chapter 6 Other Important Ligands 136
6-1 Complexes Containing M–C, M=C, and MC Bonds 136
6-2 Hydride and Dihydrogen Complexes 152
6-3 Phosphines and Related Ligands 155
6-4 Fullerene Ligands 160
6-5 Mass Spectra 165
Chapter 7 Organometallic Reactions I:

Reactions That Occur at the Metal 176
7-1 Ligand Substitution 178
7-2 Oxidative Addition 202
7-3 Reductive Elimination 226
Chapter 8 Organometallic Reactions II: Reactions

Involving Modi cation of Ligands 244
8-1 Insertion and Deinsertion 244
8-2 Nucleophilic Addition to the Ligand 267
8-3 Nucleophilic Abstraction 285
8-4 Electrophilic Reactions 289
Chapter 9 Homogeneous Catalysis: The Use
of Transition Metal Complexes
in Catalytic Cycles 311
9-1 Fundamental Concepts of Homogeneous Catalysis 312
9-2 The Hydroformylation Reaction 322
9-3 The Wacker–Smidt Synthesis of Acetaldehyde 340
9-4 Hydrogenation 350
9-5 Carbonylation of Methanol 361
9-6 Hydrocyanation 367
9-7 Specialty Chemicals 375
Chapter 10 Transition Metal–Carbene and –Carbyne
Complexes: Structure, Preparation,
and Chemistry 393
10-1 Structure of Metal Carbenes 394
10-2 Synthesis of Metal Carbene Complexes 407
10-3 Reactions of Metal–Carbene Complexes 419
10-4 Metal–Carbyne Complexes 439

Chapter 11 Metathesis and Polymerization Reactions 456
11-1 π Bond Metathesis 456
11-2 Alkyne Metathesis 486
11-3 Ziegler–Natta and Related Polymerizations of Alkenes 492
11-4 σ Bond Metathesis 507
Chapter 12 Applications of Organometallic Chemistry

to Organic Synthesis 522
12-1 Enantioselective Functional Group Interconversions 524
12-2 Carbon-Carbon Bond Formation via Nucleophilic
Attack on a η3

–π Ligand: The Tsuji–Trost Reaction 555

12-3 Carbon-Carbon Bond Formation via Carbonyl
and Alkene Insertion 567
12-4 Carbon-Carbon Bond Formation via
Transmetalation Reactions (Cross-Coupling
Reactions) 584
12-5 Carbon-Carbon Bond Formation through
Cyclization Reactions 613
Chapter 13 Isolobal Groups and Cluster Compounds 640
13-1 The Isolobal Analogy 640
13-2 Cluster Compounds 650
Appendix A List of Abbreviations A-1
Appendix B Answers to Exercises A-5
Index I-1
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