Aqueous Organometallic Chemistry and Catalysis PDF
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Aqueous Organometallic Chemistry and Catalysis NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scienti"fic Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and Physical Sciences Kluwer Academic Publishers D Behavioural and Social Sciences Dordrecht, Boston and London E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change PARTNERSHIP SUB-SERIES 1. Disarmament Technologies Kluwer Academic Publishers 2. Environment Springer-Verlag / Kluwer Academic Publishers 3. High Technology Kluwer Academic Publishers 4. Science and Technology Policy Kluwer Academic Publishers 5. Computer Networking Kluwer Academic Publishers The Partnership Sub-Series incorporates activities undertaken in collaboration with NA TO's Cooperation Partners, the countries of the CIS and Central and Eastern Europe, in Priority Areas of concern to those countries. NATo-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 50000 contributions from international scientists published in all . sections of the NATO ASI Series. Access to the NATo-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCo-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy. - via CD-ROM "NATO-PCo-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO PCO, Overijse, Belgium. Series 3: High Technology - Vol. 5 Aqueous Organometallic Chemistry and Catalysis edited by Istvan T. Horvath Corporate Research Laboratories, Exxon Research and Engineering Company, Annandale, New Jersey, U.SA and Ferenc Jo6 Institute of Physical Chemistry, Lajos Kossuth University, Debrecen, Hungary Springer Science+Business Media, BV. Proceedings of the NATO Advanced Research Workshop on Aqueous Organometallic Chemistry and Catalysis Debrecen, Hungary August 29-September 1, 1994 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-94-010-4158-4 ISBN 978-94-011-0355-8 (eBook) DOI 10.1007/978-94-011-0355-8 Printed on acid-free paper AII Rights Reserved © 1995 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1995 Softcover reprint of the hardcover 1s t edition 1995 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. TABLE OF CONTENTS Preface ix Acknowledgments xi NATO Advanced Research Workshop on Aqueous Organometallic Chemistry and Catalysis in Debrecen, Hungary xiii I. T. Horvath The Catalytic Properties of Water Soluble Phosphine Complexes xv M. T.Beck Early Work on Catalysis by Water Soluble Transition Metal Phosphine Complexes xvii F. J06 Summary of the R'bund Table Discussion of the State of the Art and Future Directions of Aqueous Organometallic Chemistry and Catalysis 1 I. T. Horvath and F. J06 Transition Metal Catalyzed Reactions of Olefins in Water: Olefm Metathesis and Isomerization 15 R. H. Grubbs Aqueous Organometallic Chemistry: Effects of a Reactive Solvent 23 F. J06, L. Nadasdi, A. Benyei, P. Csiba and A. Kath6 Aqueous Chemistry and Catalytic Activity of Organometallic Iridium Complexes 33 J. S. Merola, T. L. Husebo, K. E. Matthews, M. A. Franks, R. Pafford, and P. Chirik vi Organometallic Radical Chemistry in Aqueous Solution 47 D. R. Tyler The Use of 1,3,5-Triaza-7-phosphaadamantane (PTA), a Water- Air Soluble, Stable Ligand, in Organometallic Chemi~try and Catalysis 61 D. J. Darensbourg, T. J. Decuir, and J. H. Reibenspies Recent Developments in Metal Catalyzed Biphasic Reactions 81 V. Grushin and H. Alper Counter Phase Transfer Catalysis by Water-Soluble Phosphine Complexes 97 T. Okano Metal-Catalyzed Hydrophosphination as a Route to Water-Soluble Phosphines 111 P. G. Pringle, D. Brewin, M. B. Smith, and K. Worboys Aqueous Media inthe Intramolecular Heck Reaction 123 D. B. Grotjahn and X. Zhang New Efficient Water-Soluble Catalysts for Two-Phase Olefm Hydroformylation 127 W. A. Herrmann, G. Albanese, R. Manetsberger, R Schmid, and C. Schwer Rhodium and Palladium Water-Soluble Complexes in the Carbonylation Reactions. Improvement in the Transfer Between the Organic and Aqueous Phases 131 F. Monteil, L. Miquel, R. Queau, and Ph. Ka1ck New Water Soluble Phosphines for Organometallic Chemistry and Catalysis in the Aqueous Phase 149 B. E. Hanson, H. Ding, T. Bartik, and B. Bartik vii Hexaaquaruthenate(ll) as Catalyst Precursor in Aqueous Organometallic Catalysis 159 A. C. Benyei Ruthenium-Catalyzed Oxidation of Chlorinated Hydrocarbons in Aqueous Medium 173 M. Bressan Hydrosoluble Ligands for a New Technology 177 E. O. Kuntz Comparative Study of Biphase Reduction of Carbonyl Compounds Catalyzed by Homogeneous and Water Soluble Ru Catalysts 183 S. Sabata, J. Vcelak., J. Hetflejs Three Approaches to Catalytic Aqueous Organometallic Chemistry Involving Water Soluble Ligands, Some Modified Cyclodextrins as Ligands, and Reactions in an Aluminophosphate Cavity 187 W. R. Jackson:J. R. Anderson, E. M. Campi, Ciptati, Q. 1. McCubbin, and Z. Yang Models for Supported Aqueous-Phase Catalysis 195 I. T6th, I. Ouo, and B. E. Hanson Stoichiometric and Exhaustive Hydrolysis ofN,N-Dialkylcarbamates 199 D. Belli Dell'Amico, F. Calderazzo, F. Marchetti, and O. Pampaloni Composite Hydrogels of the Polysaccharide/Polyvalent Metal Type 211 T. Spychaj and A. Bartkowiak Organometallic Catalysis in Water and in a Two-Phase System 215 D. Sinou viii Chiral Sulfonated Phosphines in Enantioselective Catalysis 231 J. Bakos Asymmetric Complex Catalysis in Micellar Systems 245 G. Oehme, I. Grassert, and N. Flach Bioorganometallic Chemistry: The Reaction of a (Tl5-Pentamethyl cyclopentadienyl)rhodium Aqua Complex with Nucleobases, Nucleosides, Nucleotides, and Oligonucleotides 259 R. H. Fish, D. P. Smith, H. Chen, M. F. Maestre, M. M. Olmstead, M. S. Eisen, and A. Haskel On Nature's Aqueous Organometallic and Radical Chemistry with B12-Derivatives 277 B. Kriiutler Catalytic Hydrogenation of Biological Membranes: The Effects on Membrane Physical State and Functions 281 L. Vfgh and F.'1-06 Aqueous ~hospholipid Dispersions as Vectors for Selective H9mogeneous Catalysis· 289 P. J. Quinn Modification of Biomembranes by Catalytic Hydrogenation L. Nadasdi, E. Papp, and F. J06 305 Subject Index 313 Author Index 317 PREFACE The development of high-tech catalytic processes based on organometallic catalysts requires an in-depth understanding of how to control structure and reactivity in the catalytic materials on the molecular level. Rapid advances in organometallic chemistry over the last twenty years have allowed us to design and prepare very sophisticated molecules, many of which are catalysts of important processes. However, the separation of such homogeneous catalysts from products remains a limiting factor in large scale application. It is now generally accepted that the use of aqueous catalysts systems is a logical approach that could overcome of the separation problems by allowing the phase separation of the products from the catalyst phase as an inherent feature of the medium. The design and synthesis of aqueous transition-metal catalysts requires broad knowledge of organometallic chemistry in water as well as of physical and chemical properties of water itself. Water is now regarded as a unique solvent for certain stoichiometric and catalytic reactions involving organometallic compounds. Because of its highly polar, protic nature water strongly influences the acid-base behavior of solutes, the formation and disruption of ion-pairs and hydrogen bonds, and the extent of hydrophobic interactions. These effects often lead to unexpected reaction rates and selectivities, but the phenomena are still not fully understood. A very important practical and environmentally beneficial aspect of the use of a separate aqueous phase in catalytic reactions producing water-insoluble products is the potential for relatively easy and complete recovery of water soluble catalysts. This could lead to the elimination of further steps for removal of traces of heavy metals from the product and to considerable savings. When we envisioned this workshop, we felt that a specialized meeting was timely, and should aid in summarizing previous findings and facilitate further progress. Many of the major contributors in this field have already individually established personal contacts. However, bringing together most of the eminent scientists in such a diverse field would further strengthen these contacts and should permit the establishment of new relationships and new patterns of thinking. ~ ~~' Istvan T. Horvath Ferenc J06 ix ACKNOWLEDGMENTS We thank the Scientific and Environmental Mfairs Division of NATO for the sponsorship of the workshop. We are especially grateful to the following companies and institutions for their financial contributions: Exxon Research and Engineering Company F. Hoffmann-LaRoche Ltd. Kossuth Lajos Tudomanyegyetem Orszagos Miiszaki Fejlesztesi Bizottsag Komyezetvedelmi es Teriiletfejlesztesi Miniszterium Magyar Tudomanyos Akademia Kersekedelmi Bank Rt., Universitas Alapitvany Vegyesz Alapitvany We thank Professor Jean-Mary Basset, Ecole Superieure de Chimie Industrielle de Lyon, France, Professor Robert H. Grubbs, California Institute of Technology, Pasadena, USA, and Professor Wolfgang A. Herrmann, Technische UniversWit Miinchen, Germany, members of the organizing committee, for their encouragement and support. Finally, this workshop would not have been possible without the assistance and encouragement of colleagues at Lajos Kossuth University and Exxon Research and Engineering Company too numerous to mention, and we are grateful to each and every one of them. xi
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