Theoretical Aspects of Homogeneous Catalysis

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April 1995



Homogeneous catalysis plays an important role both in the laboratory and in the industry. Successful applications in industry involve new polymerisation processes with complexes of zirconium and related metals, new carbonylation processes employing palladium and rhodium, ring opening polymerisations, and new enantioselective isomerisation catalysts as in the preparation of menthol. Also in the synthesis of organic compounds in the laboratory highly selective homogeneous catalysts represent an irreplaceable part of the toolbox of the synthetic chemist. Examples of such reactions are cross-coupling (Ni, Pd), nucleophilic substitution of allylpalladium complexes, Heck reactions (Pd), asymmetric epoxidation, Wacker type reactions (Pd), asymmetric hydrogenations (Rh, Ru), reactions of chromium complexes, enantioselective reactions with Lewis acids, reactions with the McMurry reagent, etc. There is hardly any multistep organic synthesis that does not involve one of these metal catalysed reactions. Most of these catalysts have been developed by empiricism. The metal catalysed processes consist of a series of elementary steps which often have been studied in isolation in organometallic chemistry. The knowl­ edge of such elementary steps - effect ofligands, anions, coordination number, valence states - has greatly contributed to the development of improved cata­ lysts for the reactions mentioned above. In addition to the empirical approach theoretical methods have given support and guidance to the development of improved processes. Often the key steps of a cycle escape from a direct ob­ servation and then theoretical contributions are even more wanted.


Preface; P.W.N.M. van Leeuwen.
1. An Introduction to Quantum Chemical Organometallic Chemistry; P.H.M. Budzelaar, J.H. van Lenthe.
2. Oxidative Addition Reactions; M.R.A. Blomberg, P.E.M. Siegbahn.
3. Alkene Migratory Insertions and C-C Bond Formations; N. Koga, K. Morokuma.
4. Carbonyl Migratory Insertions; N. Koga, K. Morokuma.
5. A Density Functional Study on the [2s+2s] Reactions in Organometallic Chemistry; E. Folga, T. Woo, T. Ziegler.
6. Wacker Reactions; A. Dedieu.
7. Epoxidation of Ethene Catalysed by Manganese(III)-chloro-porphyrin; R. Zwaans, J.H. van Lenthe, D.H.W. den Boer.


`... the book will fill a gap in organometallic chemistry, it provides a good review for the theoretical chemist and should stimulate the practical chemist and the advanced student. The style of all contributions is clear and easy to read ... The book is recommended to anyone interested in the theoretical understanding of chemical phenomena. It is a book to motivate.'
Zeitschrift für Physikalische Chemie, 195 (1996)

` ... provides a variety of excellent examples of the power of modern theory to investigate and to provide insight into the mechanisms of important reaction mechanisms of relatively complex molecular systems. It illustrates the strength of modern theoretical analysis to deal with real-world chemical reactions and clearly confirms that the gap between theoreticians and experimentalists in this area is rapidly narrowing. I strongly recommend this book to those interested in understanding organometallic catalytic processes.'
Applied Organometallic Chemistry, 11 (1997)
EAN: 9780792331070
ISBN: 0792331079
Untertitel: Applications of Ab Initio Molecular Orbital Theory. 1995. Auflage. Book. Sprache: Englisch.
Verlag: Springer
Erscheinungsdatum: April 1995
Seitenanzahl: 230 Seiten
Format: gebunden
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