9789056992897

Transition Metal Carbonyl Cluster Chemistry

by ;
  • ISBN13:

    9789056992897

  • ISBN10:

    9056992899

  • Edition: 1st
  • Format: Hardcover
  • Copyright: 2000-11-17
  • Publisher: CRC Press

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Summary

Transition metal carbonyl clusters (TMCCs) continue to inspire great interest in chemical research, as much for their fascinating structures as for potential industrial applications conferred by their unique properties. This highly accessible book introduces the bonding, structure, spectroscopic properties, and characterization of clusters, and then explores their synthesis, reactivity, reaction mechanisms and use in organic synthesis and catalysis. Transition Metal Carbonyl Cluster Chemistrydescribes models and rules that correlate cluster structure with electron count, which are then applied in worked examples. Subsequent chapters explain how bonding relates to molecular structure, demonstrate the use of spectroscopic techniques such as NMR, IR and MS in cluster chemistry, and outline the factors contributing to the stability, dynamics and reactivity of clusters. The second part of this book discusses the synthesis and applications of TMCCs. It emphasizes the differences between the reactivities of clusters vs. mononuclear metal complexes, contingent to the availability of multiple-bonding sites and heterosite reactivity. The final chapters discuss reactions in which clusters act as homogeneous catalysts; including discussion on the use of solid and biphasic liquid-liquid supported clusters in heterogeneous catalysts. A useful reference for those commencing further research or post-graduate study on metal carbonyl clusters and advanced organometallic chemistry, this book is also a cornerstone addition to academic and libraries as well as private collections.

Author Biography

Paul J. Dyson began his research career at the University of Cambridge. before moving to the University of Edinburgh. In 1994 he moved to Imperial College as a fixed-term lecturer and in 1995 was awarded a Royal Society University Research Fellowship and is now based at the University of York J. Scott McIndoe took his BSc, MSc and DPhil at the University of Waikato before moving to Cambridge to take up a postdoctoral position. He is now a lecturer at Trinity and Newnham Colleges, Cambridge

Table of Contents

Foreword ix
Preface xi
Introduction
1(6)
Definition and Scope
1(2)
Transition Metal Carbonyl Clusters
3(4)
When Does a Cluster Become Metal-like?
4(1)
Growth in Transition Metal Carbonyl Cluster Chemistry
5(2)
Electron Counting and Metal-Metal Bonding
7(18)
The Ligands
7(1)
The Eighteen-Electron Rule
8(4)
The Effective Atomic Number (EAN) Rule
12(3)
Wade's Rules
15(1)
The Isolobal Principle
16(3)
Polyhedral Skeletal Electron Pair Theory (PSEPT)
19(2)
The Capping Principle
21(1)
Condensed Polyhedra
22(3)
Structure
25(18)
Mononuclear and Dinuclear Complexes
25(1)
Trinuclear and Tetranuclear Clusters
26(3)
Pentanuclear and Hexanuclear Clusters
29(2)
Capped Polyhedra
31(4)
Coupled and Condensed Polyhedra
35(3)
Open and Planar Clusters
38(1)
Larger Clusters
39(1)
Clusters with Metal-Metal Multiple Bonds
40(3)
Ligands
43(18)
Carbon Monoxide
43(4)
Bonding Modes of CO
44(2)
Other Effects
46(1)
Ligands Related to CO
47(1)
Phosphorus Ligands
47(4)
Interstitial Main Group Atoms
51(2)
Hydride Ligands
53(1)
Unsaturated Organic Ligands
54(3)
Alkene and Alkyne Ligands
54(1)
Unsaturated Rings
55(2)
Other Ligands
57(4)
Characterisation Techniques
61(12)
Infrared Spectroscopy
61(1)
Mass Spectrometry
62(1)
Nuclear Magnetic Resonance Spectroscopy
63(3)
1H NMR Spectroscopy
63(1)
Variable-temperature NMR Spectroscopy
64(1)
13C NMR Spectroscopy
64(2)
X-ray Crystallography
66(4)
Representations of X-ray Structures
67(1)
Disorder
68(2)
Neutron Diffraction
70(1)
Miscellaneous Characterisation Techniques
70(1)
Electron Paramagnetic Resonance Spectroscopy
70(1)
UV-visible Spectroscopy
70(1)
Mossbauer Spectroscopy
71(1)
Cluster-surface Analogy
71(2)
Synthesis
73(16)
Simple Homoleptic Carbonyls
73(3)
High Nuclearity Carbonyl Clusters
76(13)
Preparation from Salts
78(1)
Thermolysis and Pyrolysis
78(5)
Reduction and Oxidation
83(2)
Redox Condensation Reactions
85(1)
Cluster Build-up Reactions from Preformed High Nuclearity Clusters
86(3)
Reactivity
89(16)
Reduction
89(3)
Protonation
92(2)
Substitution
94(2)
Association and Dissociation
96(2)
Oxidative Addition and Reductive Elimination
98(2)
Carbide Formation
100(2)
Cluster Decomposition Reactions
102(3)
Reactions with Organic Ligands
105(16)
Alkyl and Alkylidyne Clusters
105(3)
Alkenes, Alkynes and Allyls
108(3)
C5 Rings
111(3)
C6-Rings
114(2)
C7 and C8-Rings
116(2)
Heterocycles
118(3)
Heteronuclear Carbonyl Clusters
121(14)
Synthesis
121(11)
Condensation Reactions
121(2)
Ligand Displacement
123(2)
Addition Reactions
125(1)
Redox Condensation
126(3)
Bridging Ligands
129(1)
Condensation with Electrophilic Capping Groups
130(1)
Serendipitous Syntheses
131(1)
Heterosite Reactivity
132(3)
Organic Transformations Using Stoichiometric and Catalytic Quantities of Clusters
135(22)
Establishing Catalysis by Clusters
135(1)
Hydrogenation Reactions
136(5)
Hydroformylation
141(3)
The Water-Gas Shift Reaction
144(2)
C-H Bond Activation and C-C Bond Formation
146(3)
Mixed-metal Clusters in Catalysis
149(3)
Supported Cluster Catalysis and Use of Non-organic Solvents
152(5)
Solid Supported Clusters
152(2)
Biphasic 'Liquid-liquid' Supports
154(3)
Further Reading 157(2)
Index 159(3)
Cluster Formula Index 162

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