Piet W.N.M. van Leeuwen and John C.

Chadwick Homogeneous Catalysts

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

Piet W.N.M. van Leeuwen and John C. Chadwick

Homogeneous Catalysts
Activity Stability Deactivation

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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Contents
Preface XI 1 1.1 1.2 1.2.1 1.2.2 1.2.3 1.2.4 1.3 1.3.1 1.3.2 1.3.2.1 1.3.2.2 1.4 1.4.1 1.4.2 1.4.3 1.4.4 1.4.5 1.4.6 1.5 1.6 1.7 1.7.1 1.7.2 1.7.3 1.8 1.8.1 1.8.2 1.9 1.9.1 1.9.2 Elementary Steps 1 Introduction 1 Metal Deposition 2 Ligand Loss 2 Loss of H, Reductive Elimination of HX 2 Reductive Elimination of C-, N-, O-Donor Fragments 5 Metallic Nanoparticles 6 Ligand Decomposition by Oxidation 7 General 7 Oxidation 7 Catalysis Using O2 7 Catalysis Using Hydroperoxides 8 Phosphines 8 Introduction 8 Oxidation of Phosphines 9 Oxidative Addition of a PC Bond to a Low-Valent Metal 11 Nucleophilic Attack at Phosphorus 16 Aryl Exchange Via Phosphonium Intermediates 19 Aryl Exchange Via Metallophosphoranes 21 Phosphites 23 Imines and Pyridines 26 Carbenes 27 Introduction to NHCs as Ligands 27 Reductive Elimination of NHCs 28 Carbene Decomposition in Metathesis Catalysts 31 Reactions of MetalCarbon and MetalHydride Bonds 36 Reactions with Protic Reagents 36 Reactions of Zirconium and Titanium Alkyl Catalysts 37 Reactions Blocking the Active Sites 38 Polar Impurities 38 Dimer Formation 39

VI

Contents

1.9.3

Ligand Metallation References 41

40

2 2.1 2.1.1 2.1.2 2.1.3 2.1.4 2.1.4.1 2.1.4.2 2.1.4.3 2.1.5 2.2 2.2.1 2.2.2 2.2.3 2.3 2.3.1 2.3.2 2.3.3 2.4 2.5 2.6

Early Transition Metal Catalysts for Olefin Polymerization 51 ZieglerNatta Catalysts 51 Introduction 51 Effect of Catalyst Poisons 52 TiCl3 Catalysts 53 MgCl2-supported Catalysts 54 MgCl2/TiCl4/Ethyl Benzoate Catalysts 54 MgCl2/TiCl4/Diester Catalysts 56 MgCl2/TiCl4/Diether Catalysts 57 Ethene Polymerization 57 Metallocenes 58 Introduction 58 Metallocene/MAO Systems 62 Metallocene/Borate Systems 66 Other Single-Center Catalysts 69 Constrained Geometry and Half-Sandwich Complexes 69 Octahedral Complexes 73 Diamide and Other Complexes 75 Vanadium-Based Catalysts 76 Chromium-Based Catalysts 80 Conclusions 82 References 83 Late Transition Metal Catalysts for Olefin Polymerization Nickel- and Palladium-based Catalysts 91 Diimine Complexes 91 Neutral Nickel(II) Complexes 94 Other Nickel(II) and Palladium(II) Complexes 98 Iron- and Cobalt-based Catalysts 98 Bis(imino)Pyridyl Complexes 98 Conclusions 101 References 102 Effects of Immobilization of Catalysts for Olefin Polymerization 105 Introduction 105 Metallocenes and Related Complexes 106 Immobilized MAO/Metallocene Systems 106 Immobilized Borane and Borate Activators 109 Superacidic Supports 110 MgCl2-Supported Systems 110 Other Titanium and Zirconium Complexes 113 91

3 3.1 3.1.1 3.1.2 3.1.3 3.2 3.2.1 3.3

4 4.1 4.2 4.2.1 4.2.2 4.2.3 4.2.4 4.3

Contents

VII

4.3.1 4.3.2 4.4 4.5 4.6 4.7 4.8

Constrained Geometry Complexes Octahedral Complexes 115 Vanadium Complexes 117 Chromium Complexes 121 Nickel Complexes 122 Iron Complexes 124 Conclusions 125 References 126

113

5 5.1 5.2 5.2.1 5.2.2 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.4 5.4.1 5.4.2 5.5 5.6

Dormant Species in Transition Metal-Catalyzed Olefin Polymerization 131 Introduction 131 ZieglerNatta Catalysts 132 Ethene Polymerization 132 Propene Polymerization 132 Metallocenes and Related Early Transition Metal Catalysts 134 CationAnion Interactions 134 Effects of AlMe3 136 Effects of 2,1-insertion in Propene Polymerization 137 Effects of Z3-allylic Species in Propene Polymerization 140 Chain Epimerization in Propene Polymerization 141 Effects of Dormant Site Formation on Polymerization Kinetics 142 Late Transition Metal Catalysts 143 Resting States in Nickel Diimine-Catalyzed Polymerization 143 Effects of Hydrogen in Bis(iminopyridyl) Iron-Catalyzed Polymerization 143 Reversible Chain Transfer in Olen Polymerization 145 Conclusions 147 References 148 Transition Metal Catalyzed Olefin Oligomerization 151 Introduction 151 Zirconium Catalysts 152 Titanium Catalysts 153 Tantalum Catalysts 156 Chromium Catalysts 157 Chromium-catalyzed Trimerization 157 Chromium-catalyzed Tetramerization of Ethene 160 Chromium-Catalyzed Oligomerization 162 Single-component Chromium Catalysts 164 Nickel Catalysts 166 Iron Catalysts 168

6 6.1 6.2 6.3 6.4 6.5 6.5.1 6.5.2 6.5.3 6.5.4 6.6 6.7

VIII

Contents

6.8 6.9

Tandem Catalysis involving Oligomerization and Polymerization 170 Conclusions 171 References 172 Asymmetric Hydrogenation 177 Introduction 177 Incubation by Dienes in Rhodium Diene Precursors 179 Inhibition by Substrates, Solvents, Polar Additives, and Impurities 181 Inhibition by Substrates: Iridium 181 Inhibition by Substrates, Additives: Rhodium 182 Inhibition by Substrates: Ruthenium 187 Inhibition by Formation of Bridged Species 190 Inhibition by Formation of Bridged Species: Iridium 191 Inhibition by Formation of Bridged Species: Rhodium 195 Inhibition by Ligand Decomposition 198 Inhibition by the Product 199 Inhibition by the Product: Rhodium 199 Ruthenium 200 Inhibition by Metal Formation; Heterogeneous Catalysis by Metals 201 Selective Activation and Deactivation of Enantiomeric Catalysts 204 Conclusions 206 References 207 Carbonylation Reactions 213 Introduction 213 Cobalt-Catalyzed Hydroformylation 214 Rhodium-Catalyzed Hydroformylation 217 Introduction of Rhodium-Catalyzed Hydroformylation Catalyst Formation 221 Incubation by Impurities: Dormant Sites 223 Decomposition of Phosphines 227 Decomposition of Phosphites 231 Decomposition of NHCs 235 Two-Phase Hydroformylation 238 Hydroformylation by Nanoparticle Precursors 244 Palladium-Catalyzed AlkeneCO Reactions 244 Introduction 244 Brief Mechanistic Overview 246

7 7.1 7.2 7.3 7.3.1 7.3.2 7.3.3 7.4 7.4.1 7.4.2 7.5 7.6 7.6.1 7.6.2 7.7 7.8 7.9

8 8.1 8.2 8.3 8.3.1 8.3.2 8.3.3 8.3.4 8.3.5 8.3.6 8.3.7 8.3.8 8.4 8.4.1 8.4.2

217

Contents

IX

8.4.3 8.4.4 8.4.5 8.5 8.5.1 8.5.2 8.5.3 8.5.4 8.5.5 8.6

Early Reports on Decomposition and Reactivation 248 Copolymerization 250 Methoxy- and Hydroxy-carbonylation 253 Methanol Carbonylation 259 Introduction 259 Mechanism and Side Reactions of the Monsanto Rhodium-Based Process 260 The Mechanism of the Acetic Anhydride Process Using Rhodium as a Catalyst 261 Phosphine-Modied Rhodium Catalysts 263 Iridium Catalysts 265 Conclusions 268 References 269 Metal-Catalyzed Cross-Coupling Reactions 279 Introduction; A Few Historic Notes 279 On the Mechanism of Initiation and Precursors 283 Initiation via Oxidative Addition to Pd(0) 283 Hydrocarbyl Pd Halide Initiators 290 Metallated Hydrocarbyl Pd Halide Initiators 293 Transmetallation 299 Reductive Elimination 303 Monodentate vs Bidentate Phosphines and Reductive Elimination 303 Reductive Elimination of CF Bonds 313 Phosphine Decomposition 316 Phosphine Oxidation 316 PC Cleavage of Ligands 317 Metal Impurities 322 Metal Nanoparticles and Supported Metal Catalysts 327 Supported Metal Catalysts 327 Metal Nanoparticles as Catalysts 330 Metal Precipitation 334 Conclusions 334 References 335 Alkene Metathesis 347 Introduction 347 Molybdenum and Tungsten Catalysts 349 Decomposition Routes of Alkene Metathesis Catalysts 349 Regeneration of Active Alkylidenes Species 356 Decomposition Routes of Alkyne Metathesis Catalysts 359 Rhenium Catalysts 363 Introduction 363

9 9.1 9.2 9.2.1 9.2.2 9.2.3 9.3 9.4 9.4.1 9.4.2 9.5 9.5.1 9.5.2 9.6 9.7 9.7.1 9.7.2 9.7.3 9.8

10 10.1 10.2 10.2.1 10.2.2 10.2.3 10.3 10.3.1

Contents

10.3.2 10.4 10.4.1 10.4.2 10.4.3 10.4.4 10.4.5 10.4.6 10.5

Catalyst Initiation and Decomposition 365 Ruthenium Catalysts 370 Introduction 370 Initiation and Incubation Phenomena 371 Decomposition of the Alkylidene Fragment 376 Reactions Involving the NHC Ligand 379 Reactions Involving Oxygenates 381 Tandem Metathesis/Hydrogenation Reactions 385 Conclusions 388 References 390 Index 397

XI

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 polyolen 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 exemplied 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.

XII

Preface

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 rst chapter. Chapters 26 cover homogeneous catalysts for olen 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 710, describe catalyst activity and stability in asymmetric hydrogenation, hydroformylation, alkene-CO reactions, methanol carbonylation, metal-catalyzed cross-coupling catalysis and, nally, alkene metathesis. We hope that the contents of this book will be valuable to many scientists working in the eld 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 Rob Duchateau, Peter Budzelaar and Nick Clment. We thank Marta Moya and Mara Jos Gutirrez for polishing the nal 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 Belt and their team for the perfect support provided throughout. February 2011 Piet W.N.M. van Leeuwen John C. Chadwick

Preface

XIII

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 Chadwick was 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 polyolen 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 Ziegler Natta 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 olen 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.