Transition Metal Carbonyl Cluster Chemistry

by Dyson; Paul J.

• ISBN13: 9789056992897
• ISBN10: 9056992899
• Format: Hardcover
• Copyright: 2000-11-17
• Publisher: CRC Press

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