Transition Metal Carbonyl Cluster Chemistry
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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 Chemistry describes 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.
Table of Contents
INTRODUCTION
Definition and Scope
Transition Metal Carbonyl Clusters
ELECTRON COUNTING AND METAL-METAL BONDING
The Ligands
The Eighteen-Electron Rule
The Effective Atomic Number (EAN) Rule
Wade’s Rules
The Isolobal Principle
Polyhedral Skeletal Electron Pair Theory (PSEPT)
The Capping Principle
Condensed Polyhedra
STRUCTURE
Mononuclear and Dinuclear Complexes
Trinuclear and Tetranuclear Clusters
Pentanuclear and Hexanuclear Clusters
Capped Polyhedra
Coupled and Condensed Polyhedra
Open and Planar Clusters
Larger Clusters
Clusters with Metal-Metal Multiple Bonds
LIGANDS
Carbon Monoxide
Ligands Related to CO
Phosphorus Ligands
Interstitial Main Group Atoms
Hydride Ligands
Unsaturated Organic Ligands
Other Ligands
CHARACTERISATION TECHNIQUES
Infrared Spectroscopy
Mass Spectrometry
Nuclear Magnetic Resonance Spectroscopy
X-ray Crystallography
Miscellaneous Characterisation Techniques
Cluster-Surface Analogy
SYNTHESIS
Simple Homoleptic Carbonyls
High Nuclearity Carbonyl Clusters
REACTIVITY
Reduction
Protonation
Substitution
Association and Dissociation
Oxidative Addition and Reductive Elimination
Carbide Formation
Cluster Decomposition Reactions
REACTIONS WITH ORGANIC LIGANDS
Alkyl and Alkylidyne Clusters
Alkenes, Alkynes and Allyls
C5-Rings
C6-Rings
C7 and C8-Rings
Heterocycles
HETERONUCLEAR CARBONYL CLUSTERS
Synthesis
Heterosite Reactivity
ORGANIC TRANSFORMATIONS USING STOICHIOMETRIC AND CATALYTIC QUANTITIES OF CLUSTERS
Establishing Catalysis by Clusters
Hydrogenation Reactions
Hydroformylation
The Water-Gas Shift Reaction
C-H Bond Activation and C-C Bond Formation
Mixed –metal Clusters in Catalysis
Supported Cluster Catalysis and Use of Non-Organic Solvents
Editorial Reviews
”…well-written and interesting, with a large number of examples, reflecting the considerable experience and expertise of the authors in this area…this book gives a good all-round coverage of TMCC chemistry that will definitely be of use to those teaching (or studying) advanced courses in cluster/organometallic chemistry.”
— R.L. Johnston, School of Chemistry, University of Birmingham, UK
”The book is rich in both conceptual illustrations and detailed descriptions of clusters…It promises to become a useful introduction for those new to the field of cluster chemistry.”
— Choice, June 2001
”Any group leader or graduate student in this field should be familiar with the entire contents of the text. The book provides an excellent summary of what one ought to know as a practicing carbonyl chemist
— Linda H. Doerrer, J. Chem. Ed., 2002, 79, 677.
”…this book gives a good all-round coverage of TMCC chemistry, that will definitely be of use to those (such as I) teaching (or studying) advanced courses in cluster organometallic chemistry, as well as to postgraduates working in the area of cluster chemistry... I think this will be a popular book among students."
— R. L. Johnston, J. Organomet. Chem., 2001, 628, 281.
”... [the authors] have succeeded in writing a textbook on carbonyl cluster chemistry that is well suited to the needs of university chemistry teaching. I shall recommend it to my students."
— Lutz H. Gade, Angew. Chem. Int. Ed., 2001, 40, 3257.
"If I was planning on teaching a course on carbonyl cluster chemistry this is the book that I would reach for first and I would have no difficulty recommending it to my students. It presents academics, postgraduates and undergraduates with a clear, concise, well written overview of the area."
– Tim Overton, Department of Chemistry, University of Hull, in Physical Sciences Educational Review, Vol. 7, No. 1
