Homogeneous Catalysts Activity - Stability -

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.

Piet van Leeuwen (1542) is groupleader at the Institute of Chemical Research of Catalonia in Tarragona, Spain, since 2004. After he received 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 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 Ziegler-Natta catalyst RD. From 2001-2009, 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.

Preface	p. xi
Elementary Steps	p. 1
Introduction	p. 1
Metal Deposition	p. 2
Ligand Loss	p. 2
Loss of H⁺, Reductive Elimination of HX	p. 2
Reductive Elimination of C-, N-, O-Donor Fragments	p. 5
Metallic Nanoparticles	p. 6
Ligand Decomposition by Oxidation	p. 7
General	p. 7
Oxidation	p. 7
Catalysis Using O₂	p. 7
Catalysis Using Hydroperoxides	p. 8
Phosphines	p. 8
Introduction	p. 8
Oxidation of Phosphines	p. 9
Oxidative Addition of a P-C Bond to a Low-Valent Metal	p. 11
Nucleophilic Attack at Phosphorus	p. 16
Aryl Exchange Via Phosphonium Intermediates	p. 19
Aryl Exchange Via Metallophosphoranes	p. 21
Phosphites	p. 23
Imines and Pyridines	p. 26
Carbenes	p. 27
Introduction to NHCs as Ligands	p. 27
Reductive Elimination of NHCs	p. 28
Carbene Decomposition in Metathesis Catalysts	p. 31
Reactions of Metal-Carbon and Metal-Hydride Bonds	p. 36
Reactions with Protic Reagents	p. 36
Reactions of Zirconium and Titanium Alkyl Catalysts	p. 37
Reactions Blocking the Active Sites	p. 38
Polar Impurities	p. 38
Dimer Formation	p. 39
Ligand Metallation	p. 40
References	p. 41
Early Transition Metal Catalysts for Olefin Polymerization	p. 51
Ziegler-Natta Catalysts	p. 51
Introduction	p. 51
Effect of Catalyst Poisons	p. 52
TiCl₃ Catalysts	p. 53
MgCl₂-supported Catalysts	p. 54
MgCl₂/TiCl₄/Ethyl Benzoate Catalysts	p. 54
MgCl₂/TiCl₄/Diester Catalysts	p. 56
MgCl₂/TiCl₄/Diether Catalysts	p. 57
Ethene Polymerization	p. 57
Metallocenes	p. 58
Introduction	p. 58
Metallocene/MAO Systems	p. 62
Metallocene/Borate Systems	p. 66
Other Single-Center Catalysts	p. 69
Constrained Geometry and Half-Sandwich Complexes	p. 69
Octahedral Complexes	p. 73
Diamide and Other Complexes	p. 75
Vanadium-Based Catalysts	p. 76
Chromium-Based Catalysis	p. 80
Conclusions	p. 82
References	p. 83
Late Transition Metal Catalysts for Olefin Polymerization	p. 91
Nickel- and Palladium-based Catalysts	p. 91
Diimine Complexes	p. 91
Neutral Nickel(II) Complexes	p. 94
Other Nickel(II) and Palladium(II) Complexes	p. 98
Iron- and Cobalt-based Catalysts	p. 98
Bis(imino)Pyridyl Complexes	p. 98
Conclusions	p. 101
References	p. 102
Effects of Immobilization of Catalysts for Olefin Polymerization	p. 105
Introduction	p. 105
Metallocenes and Related Complexes	p. 106
Immobilized MAO/Metallocene Systems	p. 106
Immobilized Borane and Borate Activators	p. 109
Superacidic Supports	p. 110
MgCl₂-Supported Systems	p. 110
Other Titanium and Zirconium Complexes	p. 113
Constrained Geometry Complexes	p. 113
Octahedral Complexes	p. 115
Vanadium Complexes	p. 117
Chromium Complexes	p. 121
Nickel Complexes	p. 122
Iron Complexes	p. 124
Conclusions	p. 225
References	p. 126
Dormant Species in Transition Metal-Catalyzed Olefin Polymerization	p. 132
Introduction	p. 131
Ziegler-Natta Catalysts	p. 132
Ethene Polymerization	p. 132
Propene Polymerization	p. 132
Metallocenes and Related Early Transition Metal Catalysts	p. 134
Cation-Anion Interactions	p. 134
Effects of AlMe₃	p. 136
Effects of 2,1-insertion in Propene Polymerization	p. 137
Effects of ¿³-allylic Species in Propene Polymerization	p. 140
Chain Epimerization in Propene Polymerization	p. 141
Effects of Dormant Site Formation on Polymerization Kinetics	p. 142
Late Transition Metal Catalysts	p. 143
Resting States in Nickel Diimine-Catalyzed Polymerization	p. 143
Effects of Hydrogen in Bis(iminopyridyl) Iron-Catalyzed Polymerization	p. 143
Reversible Chain Transfer in Olefin Polymerization	p. 145
Conclusions	p. 147
References	p. 148
Transition Metal Catalyzed Olefin Oligomerization	p. 151
Introduction	p. 151
Zirconium Catalysts	p. 152
Titanium Catalysts	p. 153
Tantalum Catalysts	p. 156
Chromium Catalysts	p. 157
Chromium-catalyzed Trimerization	p. 157
Chromium-catalyzed Tetramerization of Ethene	p. 160
Chromium-Catalyzed Oligomerization	p. 162
Single-component Chromium Catalysts	p. 164
Nickel Catalysts	p. 166
Iron Catalysts	p. 168
Tandem Catalysis involving Oligomerization and Polymerization	p. 170
Conclusions	p. 171
References	p. 172
Asymmetric Hydrogenation	p. 177
Introduction	p. 177
Incubation by Dienes in Rhodium Diene Precursors	p. 179
Inhibition by Substrates, Solvents, Polar Additives, and Impurities	p. 181
Inhibition by Substrates: Iridium	p. 181
Inhibition by Substrates, Additives: Rhodium	p. 182
Inhibition by Substrates: Ruthenium	p. 187
Inhibition by Formation of Bridged Species	p. 190
Inhibition by Formation of Bridged Species: Iridium	p. 191
Inhibition by Formation of Bridged Species: Rhodium	p. 195
Inhibition by Ligand Decomposition	p. 198
Inhibition by the Product	p. 199
Inhibition by the Product: Rhodium	p. 199
Ruthenium	p. 200
Inhibition by Metal Formation; Heterogeneous Catalysis by Metals	p. 201
Selective Activation and Deactivation of Enantiomeric Catalysts	p. 204
Conclusions	p. 206
References	p. 207
Carbonylation Reactions	p. 213
Introduction	p. 213
Cobalt-Catalyzed Hydroformylation	p. 214
Rhodium-Catalyzed Hydroformylation	p. 217
Introduction of Rhodium-Catalyzed Hydroformylation	p. 217
Catalyst Formation	p. 221
Incubation by Impurities: Dormant Sites	p. 223
Decomposition of Phosphines	p. 227
Decomposition of Phosphites	p. 231
Decomposition of NHCs	p. 235
Two-Phase Hydroformylation	p. 238
Hydroformylation by Nanoparticle Precursors	p. 244
Palladium-Catalyzed Alkene-CO Reactions	p. 244
Introduction	p. 244
Brief Mechanistic Overview	p. 246
Early Reports on Decomposition and Reactivation	p. 248
Copolymerization	p. 250
Methoxy- and Hydroxy-carbonylation	p. 253
Methanol Carbonylation	p. 259
Introduction	p. 259
Mechanism and Side Reactions of the Monsanto Rhodium-Based Process	p. 260
The Mechanism of the Acetic Anhydride Process Using Rhodium as a Catalyst	p. 261
Phosphine-Modified Rhodium Catalysts	p. 263
Iridium Catalysts	p. 265
Conclusions	p. 268
References	p. 269
Metal-Catalyzed Cross-Coupling Reactions	p. 279
Introduction; A Few Historic Notes	p. 279
On the Mechanism of Initiation and Precursors	p. 283
Initiation via Oxidative Addition to Pd(0)	p. 283
Hydrocarbyl Pd Halide Initiators	p. 290
Metallated Hydrocarbyl Pd Halide Initiators	p. 293
Transmetallation	p. 299
Reductive Elimination	p. 303
Monodentate vs Bidentate Phosphines and Reductive Elimination	p. 303
Reductive Elimination of C-F Bonds	p. 313
Phosphine Decomposition	p. 316
Phosphine Oxidation	p. 316
P-C Cleavage of Ligands	p. 317
Metal Impurities	p. 322
Metal Nanoparticles and Supported Metal Catalysts	p. 327
Supported Metal Catalysts	p. 327
Metal Nanoparticles as Catalysts	p. 330
Metal Precipitation	p. 334
Conclusions	p. 334
References	p. 335
Alkene Metathesis	p. 347
Introduction	p. 347
Molybdenum and Tungsten Catalysts	p. 349
Decomposition Routes of Alkene Metathesis Catalysts	p. 349
Regeneration of Active Alkylidenes Species	p. 356
Decomposition Routes of Alkyne Metathesis Catalysts	p. 359
Rhenium Catalysts	p. 363
Introduction	p. 363
Catalyst Initiation and Decomposition	p. 365
Ruthenium Catalysts	p. 370
Introduction	p. 370
Initiation and Incubation Phenomena	p. 371
Decomposition of the Alkylidene Fragment	p. 376
Reactions Involving the NHC Ligand	p. 379
Reactions Involving Oxygenates	p. 381
Tandem Metathesis/Hydrogenation Reactions	p. 385
Conclusions	p. 388
References	p. 390
Index	p. 397
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Homogeneous Catalysts Activity - Stability - Deactivation

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