The Organometallic Chemistry of the Transition Metals, 4th Edition

by Robert H. Crabtree (Yale University)

• ISBN13: 9780471662563
• ISBN10: 0471662569
• Edition: 4th
• Format: Hardcover
• Copyright: 2005-05-01
• Publisher: Wiley-Interscience

Summary

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.

Author Biography

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).

Table of Contents

Preface	ix
List of Abbreviations	xi
1 Introduction	1	(28)
1.1 Werner Complexes,	2	(4)
1.2 The Trans Effect,	6	(2)
1.3 Soft Versus Hard Ligands,	8	(1)
1.4 The Crystal Field,	9	(5)
1.5 The Ligand Field,	14	(1)
1.6 Back Bonding,	15	(4)
1.7 Electroneutrality,	19	(2)
1.8 Types of Ligand,	21	(8)
2 General Properties of Organometallic Complexes	29	(24)
2.1 The 18-Electron Rule,	30	(5)
2.2 Limitations of the 18-Electron Rule,	35	(2)
2.3 Electron Counting in Reactions,	37	(2)
2.4 Oxidation State,	39	(2)
2.5 Coordination Number and Geometry,	41	(4)
2.6 Effects of Complexation,	45	(2)
2.7 Differences between Metals,	47	(2)
2.8 Outer-Sphere Coordination,	49	(4)
3 Metal Alkyls, Aryls, and Hydrides and Related σ-Bonded Ligands	53	(34)
3.1 Transition Metal Alkyls and Aryls,	53	(15)
3.2 Related σ-Bonded Ligands,	68	(4)
3.3 Metal Hydride Complexes,	72	(3)
3.4 σ Complexes,	75	(4)
3.5 Bond Strengths for Classical σ-Bonding Ligands,	79	(8)
4 Carbonyls, Phosphine Complexes, and Ligand Substitution Reactions	87	(38)
4.1 Metal Complexes of CO, RNC, CS, and NO,	87	(12)
4.2 Phosphines and Related Ligands,	99	(5)
4.3 Dissociative Substitution,	104	(5)
4.4 Associative Mechanism,	109	(3)
4.5 Redox Effects, the I Mechanism, and Rearrangements in Substitution,	112	(3)
4.6 Photochemical Substitution,	115	(3)
4.7 Steric and Solvent Effects in Substitution,	118	(7)
5 Complexes of π-Bound Ligands	125	(34)
5.1 Alkene and Alkyne Complexes,	125	(6)
5.2 Allyl Complexes,	131	(5)
5.3 Diene Complexes,	136	(4)
5.4 Cyclopentadienyl Complexes,	140	(8)
5.5 Arenes and Other Alicyclic Ligands,	148	(4)
5.6 Metalacycles and Isoelectronic and Isolobal Replacement,	152	(2)
5.7 Stability of Polyene and Polyenyl Complexes,	154	(5)
6 Oxidative Addition and Reductive Elimination	159	(24)
6.1 Concerted Additions,	162	(3)
6.2 SN² Reactions,	165	(1)
6.3 Radical Mechanisms,	166	(3)
6.4 Ionic Mechanisms,	169	(1)
6.5 Reductive Elimination,	170	(6)
6.6 σ-Bond Metathesis,	176	(1)
6.7 Oxidative Coupling and Reductive Cleavage,	177	(6)
7 Insertion and Elimination	183	(24)
7.1 Reactions Involving CO,	185	(6)
7.2 Insertions Involving Alkenes,	191	(6)
7.3 Other Insertions,	197	(2)
7.4 α,β,γ, and δ Elimination,	199	(8)
8 Nucleophilic and Electrophilic Addition and Abstraction	207	(28)
8.1 Nucleophilic Addition to CO,	210	(3)
8.2 Nucleophilic Addition to Polyene and Polyenyl Ligands,	213	(8)
8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls,	221	(1)
8.4 Electrophilic Addition,	222	(4)
8.5 Electrophilic Abstraction of Alkyl Groups,	226	(2)
8.6 Single-Electron Transfer Pathways,	228	(1)
8.7 Reactions of Organic Free Radicals with Metal Complexes,	229	(6)
9 Homogeneous Catalysis	235	(40)
9.1 Alkene Isomerization,	239	(2)
9.2 Alkene Hydrogenation,	241	(13)
9.3 Alkene Hydroformylation,	254	(3)
9.4 Hydrocyanation of Butadiene,	257	(4)
9.5 Alkene Hydrosilation and Hydroboration,	261	(2)
9.6 Coupling Reactions,	263	(3)
9.7 Surface and Supported Organometallic Catalysis,	266	(9)
10 Physical Methods in Organometallic Chemistry	275	(34)
10.1 Isolation,	275	(1)
10.2 ¹H NMR Spectroscopy,	276	(5)
10.3 ¹³C NMR Spectroscopy,	281	(1)
10.4 ³¹P NMR Spectroscopy,	282	(2)
10.5 Dynamic NMR,	284	(4)
10.6 Spin Saturation Transfer,	288	(2)
10.7 T1 and the Nuclear Overhauser Effect,	290	(4)
10.8 Isotopic Perturbation of Resonance,	294	(3)
10.9 IR Spectroscopy,	297	(3)
10.10 Crystallography,	300	(2)
10.11 Other Methods,	302	(7)
11 Metal-Ligand Multiple Bonds	309	(34)
11.1 Carbenes,	309	(16)
11.2 Carbynes,	325	(2)
11.3 Bridging Carbenes and Carbynes,	327	(3)
11.4 N-Heterocyclic Carbenes,	330	(4)
11.5 Multiple Bonds to Heteroatoms,	334	(9)
12 Applications of Organometallic Chemistry	343	(36)
12.1 Alkene Metathesis,	343	(7)
12.2 Dimerization, Oligomerization, and Polymerization of Alkenes,	350	(10)
12.3 Activation of CO and CO2,	360	(4)
12.4 CH Activation,	364	(7)
12.5 Organometallic Materials and Polymers,	371	(8)
13 Clusters and the Metal-Metal Bond	379	(38)
13.1 Structures,	380	(13)
13.2 The Isolobal Analogy,	393	(4)
13.3 Synthesis,	397	(2)
13.4 Reactions,	399	(8)
13.5 Giant Clusters and Nanoparticles,	407	(4)
13.6 Giant Molecules,	411	(6)
14 Applications to Organic Synthesis	417	(46)
14.1 Metal Alkyls Aryls, and Hydrides,	418	(11)
14.2 Reduction, Oxidation, and Control of Stereochemistry,	429	(6)
14.3 Protection and Deprotection,	435	(3)
14.4 Reductive Elimination and Coupling Reactions,	438	(5)
14.5 Insertion Reactions,	443	(4)
14.6 Nucleophilic Attack on a Ligand,	447	(7)
14.7 Heterocycles,	454	(1)
14.8 More Complex Molecules,	455	(8)
15 Paramagnetic, High-Oxidation-State, and High-Coordination-Number Complexes	463	(28)
15.1 Magnetism and Spin States,	464	(7)
15.2 Polyalkyls,	471	(5)
15.3 Polyhydrides,	476	(3)
15.4 Cyclopentadienyl Complexes,	479	(2)
15.5 f -Block Complexes,	481	(10)
16 Bioorganometallic Chemistry	491	(30)
16.1 Introduction,	492	(5)
16.2 Coenzyme B12,	497	(6)
16.3 Nitrogen Fixation,	503	(6)
16.4 Nickel Enzymes,	509	(8)
16.5 Biomedical Applications,	517	(4)
Useful Texts on Allied Topics	521	(2)
Major Reaction Types	523	(2)
Solutions to Problems	525	(14)
Index	539