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Catalysis in C 1 Chemistry Catalysis by Metal Complexes CATALYSIS IN C 1 CHEMISTRY CATALYSIS BY METAL COMPLEXES Editors: R. UGO, University of Milan, Milan, Italy B. R. J AMES, University of British Columbia, Vancouver, Canada Advisory Board: J. L. GARNETT, University ofNew South Wales,Kensington,Australia L. MARKO, Hungarian Academy of Sciences, Veszprem, Hungary ICHIRO MORIT ANI, Osaka University, Osaka, Japan W. ORME-J OHNSON, Massachusetts Institute of Technology, Cambridge, Mass., U.S.A. R. L. RICHARDS, University of Sussex, Brighton, England C. A. TOLMAN, E. I. du Pont de Nemours Comp., Inc., Wilmington, Del., U.S.A. VOLUME 4 CATALYSIS IN C1 CHEMISTRY Edited by WILHELM KEIM Institut fur Technische Chemie und Petrolchemie der R WTH, Aachen D. REIDEL PUBLISHINGtt... COMPANY A MEMBER OF THE KLUWER " ACADEMIC PUBLISHERS GROUP DORDRECHT/BOSTON/LANCASTER Library of Congress Cataloging in Publication Data Main en try under title: Catalysis in C l Chemistry. (Catalysis by Metal Complexes: v. 4) Bibliography: p. Includes index. 1. Carbon compounds. 2. Catalysis. 1. Keirn, Wilhelm, 1934- II. Series. QD281.C3C36 1983 546:681595 83-9593 ISBN-13: 978-94-009-7042-7 e-ISBN-13: 978-94-009-7040-3 001: 10. 1007/978-94-009-7040-3 Published by D. Reidel Publishing Company, P.O. Box 17, 3300 AA Dordrecht, Holland. Sold and distributed in the U.S.A. and Canada by Klu\ler Academic Publishers 190 Old Derby Street, Hingham, MA 02043, U.S.A. In all other countries. sold and distribu ted by Kluwer Academic Publishers Group, P.O. Box 322,3300 AH Dordrecht, Holland. All Rights Reserved Copyright © 1983 by D. Reidel Publishing Company, Dordrecht, Holland Sottcover reprint of the hardcover I st edition 1983 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 photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner TABLE OF CONTENTS PREFACE xi INTRODUCTION W. K E 1M: Homogeneous Carbon Monoxide Hydrogenation 5 1. Stoichiometric CO Reduction (Model Reactions) 5 1.1. CO Coordination 6 1.2. CO Activation (Scission and CH Bond Formation) 8 1.2.1. CO Activation via Formyl Complexes 12 1.2.2. CO Activation via Hydroxymethyl, Hydroxymethy- lene Intermediates 14 1.2.3. CO Activation via Carbide, Carbyne, Carbene Inter- mediates 15 1.3. Formation of C 1 + Species (Growth Products) 19 1.3.1. Growth by Metal-C-C Bond Formation 19 1.3 .2. Growth by Metal-O-C Bond Formation 25 1.3.3. Growth by Aldehydes as Intermediates 26 2. Catalytic Homogeneous Reduction of Carbon Monoxide 26 2.1. Reduction of CO with Reducing Agents Other than Molecular Hydrogen 27 2.2. Direct Reduction of CO with Hydrogen 29 References 35 M. RbpER: Fischer-TropschSynthesis 41 1. Introduction 41 2. Historic Developments in Heterogeneous Carbon Monoxide Hydrogenation 43 3. Technical Realization of the Fischer-Tropsch Synthesis 45 3.1. Type's of Industrial Reactors 45 3.2. Integrated Structures of Production Plants 48 4. Basic Features of the Fischer-Tropsch Reaction 49 4.1. Stoichiometry 50 4.2. Thermodynamics 51 v vi T ABLE OF CONTENTS 4.3. Molecular Weight Distribution of Products 52 4.4. Catalysts 55 4.4.1. Catalyst Metals 55 4.4.2. Promoters 56 4.4.3. Supports 58 4.4.4. Poisons 59 4.4.5. Preparation, Activation and Performance of Catalysts 59 4.5. Surface Species 64 5. Product Selectivity Control 68 5.1. Control of Molecular Weight Distribution 69 5.2. Selective Manufacture of Ole fins 71 5.3. Selective Manufacture of Alcohols 72 6. Mechanistic Considerations 75 6.1. The Carbide Mechanism 75 6.2. The Hydroxycarbene Mechanism 78 6.3. Carbon Monoxide Insertion Mechanisms 79 6.4. Evaluation of the Proposed Mechanisms 82 7. Conclusions 83 References 83 W. KEIM: i'v!ethallol Buildillg Block for Chcmicals 89 1. Mechanism of CO Reduction to Methanol 90 2. Future Use of Methanol 93 2.1. Methanol: Raw Material for the Chemical Industry 94 2.1.1. Base Chemicals from Methanol 94 2.1.1.1. Olefins and aromatics 94 2.1.1.2. Generation of pure hydrogen 96 2.1.1.3. Generation of pure CO 97 2.1.1.4. Synthesis of styrene 97 2.1.2. Fine Chemicals from Methanol 97 2.1.2.1. Aceticanhydride 99 2.1.2.2. Vinylacetate 100 2.1.2.3. Ethylene glycol 100 2.1.2.4. Methyl methacrylate 101 2.1.2.5. Methyl formate 102 References 102 M. ROPER AND H. LOEVENICH: The Homologation of Methanol 105 1. Introduction 105 1.1. Principle of the Homologation Reaction 105 1.2. Potential Use of Methanol Homologation 106 TABLE OF CONTENTS vii 2. Cobalt-Catalyzed Methanol Homologation 107 2.1. Historic Developments and Recent Progress 107 2.2. Parameters Controlling the Homologation Reaction 108 2.2.1. Influence of Catalyst Composition 109 2.2.1.1. Nature of the cobalt compound 109 2.2.1.2. Promoters 112 2.2.1.3. Ligands 113 2.2.1.4. Cometals as hydrogenation catalysts 115 2.2.2. Influence of Reaction Conditions 116 2.2.2.1. Solvents 117 2.2.2.2. CO/H 2 ratio 117 2.2.2.3. Syngas pressure 117 2.2.2.4. Reaction temperature 117 2.2.2.5 Reaction time 119 2.3. Possible Reaction Mechanisms 120 2.3.1. Nonpromoted Cobalt Catalysts 120 2.3.2. Iodine-Promoted Cobalt Catalysts 123 2.3.3. Hydrogenation of Acetaldehyde to Ethanol 126 2.3.4. Side-product Formation 127 3. Other Ca talyst Metals 127 3.1. Iron Catalysts 128 3.2. Ruthenium Catalysts 129 3.3. Rhodium Catalysts 130 4. Conclusions 131 References 131 R. UGO: Hydrofonnylation and Carbonylation Reactions 135 1. Hydroformylation and Carbonylation of Unsaturated Organic Substrates 135 1.1. Introduction 135 1.2. Reppe-Type Chemistry 137 1 .2.1. Alkyne Carbonyla tion 137 1.2.2. Alkene Carbonylation 140 1.3. The Hydroformylation Reaction 141 1.3.1. Unmodified Cobalt Carbonyl Systems 142 1.3 .2. Phosphine-Modified Cobalt Carbonyl Systems 145 1 .3.3. Rhodium Ca talysts 147 1.4. General Mechanistic Implications 150 1.5. Carbonylation in Acidic Conditions 155 2. Carbonylation Under Oxidative Conditions 156 2.1. Introduction 156 viii TABLE OF CONTENTS 2.2. The Synthesis of Oxalates 157 2.3. The Synthesis of Acrylates and Related Derivatives 162 2 A. The Synthesis of Carbonates 165 References 167 A. BEHR: Activation of Carbon Dioxide viiI Coordination to Transi- tion Metal Complexes 169 1. Introduction 169 2. Insertion of Carbon Dioxide into Transition Metal Complexes 170 2.l. Insertion into M-C Bonds 170 2.2. Insertion into M-H Bonds 175 2.3. Insertion into M-O Bonds 178 204. Insertion into M-N Bonds 180 3. Transition Metal-Catalyzed Syntheses Involving Carbon Dioxide 183 3.1. Reactions of CO 2 with Hydrogen and Further Reaction Components 183 3.2. Reactions of CO 2 with Unsaturated Hydrocarbons 189 3.2.1. Alkynes 189 3.2.2. Alkenes 191 3.2.3. Dienes 191 3.2 A. Methylenecyclopropanes 194 3.3. Reactions of CO 2 with Strained Heterocycles 195 4. Deoxygenation of CO2 199 5. Dimerization of CO2 203 6. Carbon Dioxide as a Cocatalyst in Homogeneous Catalysis 205 6.1. Dimerization 205 6.2. Telomerization 206 6.3. Metathesis 206 604. Hydroformylation 207 6.5. Polymerization 207 7. Conclusions 207 8. Glossary of Nonstandard Abbreviations 207 References 208 A. J. HUBERT AND E. PUENTES: Hydrocyanation 219 I. Introduction 219 1.1. Application of HCN and its Derivatives 219 1.2. Preparation of HCN 220 1 .3. Properties of HCN 221 1.4. Coordination Modes of HCN 221 TABLE OF CONTENTS ix 2. Reaction of HCN with Multiple Bonds 223 2.l. Hydrocyanation of Unsaturated Hydrocarbons 223 2.1.l. Hydrocyanation of Acetylene 223 2.1.2. Hydrocyanation of Olefins 223 2.1.2.1. Activation of HeN by cuprous salts 228 2.1.2.2. Selectivity of hydrocyanation reactions 229 2.1.2.3. Oxycyanation of olefins 230 2.1.2.4. Reaction with L4-butenediol 230 2.1.2.5. Reaction of cyanogen with hydrocarbons 231 2.1.3. Isonitrile Synthesis by Hydrocyanation 231 2.2. Hydrocyanation of Functionalized Olefins 231 2.3. Hydrocyanation of C=O and C=N Double Bonds 234 3. Applications of HCN in Organic Chemistry Other than Addition to Multiple Bonds 236 3.1. Cyanogen Chemistry 236 3.2. Oxamide Synthesis 238 3.3. Cyclotrimerization of HCN and of its Derivatives 238 3.4. Polymerization of HCN 239 3.5. Formamide Synthesis 241 3.6. Oxidation and Hydrogenation of HCN 241 4. Physiological Properties of HCN and Safety 241 References 242 A. J. HUBERT: Methane 245 1. Methane 245 1.1. Industrial and Synthetic Applications of Methane 245 1.1.1. Synthesis Gas 245 1.1.2. Halogenation of Methane 246 1.1.3. Hydrocyanic Acid Production 247 1.1.4. Acetylene Production 248 1 .1 .5. Pa rticular Reactions 248 1 .1 .5.1. N it riles synt hesis 248 1.1.5.2. Direct synthesis of methanol and formal- ~~~ M8 1.1.5.3. Carboxylation of methane 249 1.1.5.4. Formation ofCS2 249 1.l.5.5. Ot her reactions 249 1.2. Activation of Methane 251 1 .2.1. Activation of Methane by Soluble Metal Complexes 251 1.2.2. Activation of Methane by Superacids 254 1.3. Methane in Nature 254 x TABLE OF CONTENTS ! Alkanes 255 2.1. Activation of Alkanes by Metal Complexes 255 2.2.
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