Homogeneous Catalysts E-Book

Piet W. N. M. van Leeuwen

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 817

Veröffentlichungsjahr: 2011

Beschreibung

This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste. The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

Leseprobe

Contents

Cover

Further reading

Title Page

Copyright

Preface

About the Author

Chapter 1: Elementary Steps

1.1 Introduction

1.2 Metal Deposition

1.3 Ligand Decomposition by Oxidation

1.4 Phosphines

1.5 Phosphites

1.6 Imines and Pyridines

1.7 Carbenes

1.8 Reactions of Metal–Carbon and Metal–Hydride Bonds

1.9 Reactions Blocking the Active Sites

References

Chapter 2: Early Transition Metal Catalysts for Olefin Polymerization

2.1 Ziegler–Natta Catalysts

2.2 Metallocenes

2.3 Other Single-Center Catalysts

2.4 Vanadium-Based Catalysts

2.5 Chromium-Based Catalysts

2.6 Conclusions

References

Chapter 3: Late Transition Metal Catalysts for Olefin Polymerization

3.1 Nickel- and Palladium-based Catalysts

3.2 Iron- and Cobalt-based Catalysts

3.3 Conclusions

References

Chapter 4: Effects of Immobilization of Catalysts for Olefin Polymerization

4.1 Introduction

4.2 Metallocenes and Related Complexes

4.3 Other Titanium and Zirconium Complexes

4.4 Vanadium Complexes

4.5 Chromium Complexes

4.6 Nickel Complexes

4.7 Iron Complexes

4.8 Conclusions

References

Chapter 5: Dormant Species in Transition Metal-Catalyzed Olefin Polymerization

5.1 Introduction

5.2 Ziegler–Natta Catalysts

5.3 Metallocenes and Related Early Transition Metal Catalysts

5.4 Late Transition Metal Catalysts

5.5 Reversible Chain Transfer in Olefin Polymerization

5.6 Conclusions

References

Chapter 6: Transition Metal Catalyzed Olefin Oligomerization

6.1 Introduction

6.2 Zirconium Catalysts

6.3 Titanium Catalysts

6.4 Tantalum Catalysts

6.5 Chromium Catalysts

6.6 Nickel Catalysts

6.7 Iron Catalysts

6.8 Tandem Catalysis involving Oligomerization and Polymerization

6.9 Conclusions

References

Chapter 7: Asymmetric Hydrogenation

7.1 Introduction

7.2 Incubation by Dienes in Rhodium Diene Precursors

7.3 Inhibition by Substrates, Solvents, Polar Additives, and Impurities

7.4 Inhibition by Formation of Bridged Species

7.5 Inhibition by Ligand Decomposition

7.6 Inhibition by the Product

7.7 Inhibition by Metal Formation; Heterogeneous Catalysis by Metals

7.8 Selective Activation and Deactivation of Enantiomeric Catalysts

7.9 Conclusions

References

Chapter 8: Carbonylation Reactions

8.1 Introduction

8.2 Cobalt-Catalyzed Hydroformylation

8.3 Rhodium-Catalyzed Hydroformylation

8.4 Palladium-Catalyzed Alkene–CO Reactions

8.5 Methanol Carbonylation

8.6 Conclusions

References

Chapter 9: Metal-Catalyzed Cross-Coupling Reactions

9.1 Introduction; A Few Historic Notes

9.2 On the Mechanism of Initiation and Precursors

9.3 Transmetallation

9.4 Reductive Elimination

9.5 Phosphine Decomposition

9.6 Metal Impurities

9.7 Metal Nanoparticles and Supported Metal Catalysts

9.8 Conclusions

References

Chapter 10: Alkene Metathesis

10.1 Introduction

10.2 Molybdenum and Tungsten Catalysts

10.3 Rhenium Catalysts

10.4 Ruthenium Catalysts

10.5 Conclusions

References

Index

Further reading

Arpe, H.-J.

Industrial Organic Chemistry

Fifth, Completely Revised Edition

2010

ISBN: 978-3-527-32002-8

Behr, A. / Neubert, P.

Applied Homogeneous Catalysis

2012

ISBN: 978-3-527-32641-9 (Hardcover)

ISBN: 978-3-527-32633-4 (Softcover)

Roberts, S. M.

Catalysts for Fine Chemical Synthesis

Volumes 1-5. Set

2007

ISBN: 978-0-470-51605-8

Platz, M. S., Moss, R. A., Jones, M. (eds.)

Reviews of Reactive Intermediate Chemistry

2007

ISBN: 978-0-471-73166-5

Sheldon, R. A., Arends, I., Hanefeld, U.

Green Chemistry and Catalysis

2007

ISBN: 978-3-527-30715-9

Dalko, P. I. (ed.)

Enantioselective Organocatalysis

Reactions and Experimental Procedures

2007

ISBN: 978-3-527-31522-2

The Authors

Prof. Dr. Piet W.N.M. van Leeuwen

Institute of Chemical Research of Catalonia (ICIQ)

Av. Paisos Catalans 16

43007 Tarragona

Spain

Dr. John C. Chadwick

University of Eindhoven

Chemical Engineering & Chemistry

P.O. Box 513

5600 MB Eindhoven

The Netherlands

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Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.

© 2011 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978-3-527-32329-6

Preface

Homogeneous catalysts have played a key role in the production of petrochemicals and coal-derived chemicals since the 1960s. In the last two decades, transition metal catalysts have revolutionized synthetic organic chemistry, both in the laboratory and in industrial production. The use of homogeneous catalysts in polyolefin synthesis started in the 1980s and triggered enormous R&D efforts, leading to hitherto inaccessible polymers and to greatly improved control over polymer structure and properties. The introduction of new processes and catalysts continues in bulk chemical production, as exemplified by new routes that have recently come on stream for the production of 1-octene and methyl methacrylate.

For all catalysts, selectivity and rates of reactions are crucial parameters and in the laboratory even the rate may not concern us that much, as catalyst loadings of 5% or more are often applied. For industrial applications, however, high turnover numbers are required for economic reasons, which may be more complex than simply catalyst costs. For the bulk chemical applications, studies of catalyst activation, activity, stability, deactivation, recycling and regeneration have always formed an integral part of catalysis research. A considerable research effort has been devoted to this, mainly in industry, but explicit publications are scarce, although some stability issues can be deduced from the patent literature. Catalyst stability has been a highly important factor in transforming advances in catalysis into practical applications, notably in the areas of polymer synthesis, cross-coupling chemistry, hydrogenation catalysis, carbonylation reactions and metathesis chemistry.

In heterogeneous catalysis, the study of activation, deactivation, and regeneration of catalysts has always been a major research activity. These topics have been addressed in many articles, books and conferences, and literature searches with these keywords give many relevant results. For homogeneous catalysts this is not the case, with the possible exception of metathesis. A wealth of knowledge can be found in a vast number of publications, but this is not easily retrieved. The approach in homogeneous catalysis is entirely different to that of heterogeneous catalysis, especially before industrial applications come into sight; in homogeneous catalysis, the general approach to improving the catalyst performance is variation of one of the catalytic components, without much attention being paid to the question of why other catalyst systems failed.

In this book, we address a number of important homogeneous catalysts, focusing on activity, stability and deactivation, including the important issue of how deactivation pathways can be avoided. Key concepts of activation and deactivation, together with typical catalyst decomposition pathways, are outlined in the first chapter. Chapters 2–6 cover homogeneous catalysts for olefin polymerization and oligomerization, including the effects of catalyst immobilization and polymerization rate limitation as a result of dormant site formation. The following sections of the book, Chapters 7–10, describe catalyst activity and stability in asymmetric hydrogenation, hydroformylation, alkene-CO reactions, methanol carbonylation, metal-catalyzed cross-coupling catalysis and, finally, alkene metathesis.

We hope that the contents of this book will be valuable to many scientists working in the field of homogeneous catalysis and that the inclusion of a broad range of topics, ranging from polymerization catalysis to the synthesis of speciality and bulk chemicals, can lead to useful cross-fertilization of ideas.

We would like to acknowledge useful comments and contributions from RobDuchateau, Peter Budzelaar and Nick Clément. We thank Marta Moya and María José Gutiérrez for polishing the final draft. We are also indebted to Manfred Kohl from Wiley-VCH, for convincing one of us at the 10th International Symposium on Catalyst Deactivation to embark on this book project. We thank him, Lesley Belfit and their team for the perfect support provided throughout.

February 2011

Piet W.N.M. van Leeuwen

John C. Chadwick

About the Authors

Piet van Leeuwen(1942) is group leader at the Institute of Chemical Research of Catalonia in Tarragona, Spain, since 2004. After receiving his PhD degree at Leyden University in 1967 he joined Shell Research in 1968. Until 1994 he headed a research group at Shell Research in Amsterdam, studying many aspects of homogeneous catalysis. He was Professor of Homogeneous Catalysis at the University of Amsterdam from 1989 until 2007. He has coauthored 350 publications, 30 patents, and many book chapters, and is author of the book Homogeneous Catalysis: Understanding the Art. He (co)directed 45 PhD theses. In 2005 he was awarded the Holleman Prize for organic chemistry by the Royal Netherlands Academy. In 2009 he received a doctorate honoris causa from the University Rovira I Virgili, Tarragona, and he was awarded a European Research Council Advanced Grant.

John Chadwickwas born in 1950 in Manchester, England and received his B.Sc. and Ph.D. degrees from the University of Bristol, after which he moved to The Netherlands, joining Shell Research in Amsterdam in 1974. He has been involved in polyolefin catalysis since the mid 1980s and in 1995 transferred from Shell to the Montell (later Basell) research center in Ferrara, Italy, where he was involved in fundamental ZieglerNatta catalyst R&D. From 2001 to 2009, he was at Eindhoven University of Technology on full-time secondment from Basell (now LyondellBasell Industries) to the Dutch Polymer Institute (DPI), becoming DPI Programme Coordinator for Polymer Catalysis and Immobilization. Until his retirement in 2010, his main research interests involved olefin polymerization catalysis, including the immobilization of homogeneous systems, and the relationship between catalyst and polymer structure. He is author or co-author of more than 60 publications and 11 patent applications.