Homogeneous Catalysts: Activity - Stability - Deactivation

412 Pages·2011·3.45 MB·English

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

Piet W.N.M. van Leeuwen
and John C. Chadwick
Homogeneous Catalysts
Further reading
Arpe, H.-J.
Industrial Organic Chemistry
Fifth,CompletelyRevisedEdition
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
Volumes1-5.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
ReactionsandExperimentalProcedures
2007
ISBN:978-3-527-31522-2
Piet W.N.M. van Leeuwen and John C. Chadwick
Homogeneous Catalysts
Activity – Stability – Deactivation
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V
Contents
Preface XI
1 ElementarySteps 1
1.1 Introduction 1
1.2 MetalDeposition 2
1.2.1 LigandLoss 2
þ
1.2.2 LossofH ,ReductiveEliminationofHX 2
1.2.3 ReductiveEliminationofC-,N-,O-DonorFragments 5
1.2.4 MetallicNanoparticles 6
1.3 LigandDecompositionbyOxidation 7
1.3.1 General 7
1.3.2 Oxidation 7
1.3.2.1 CatalysisUsingO 7
2
1.3.2.2 CatalysisUsingHydroperoxides 8
1.4 Phosphines 8
1.4.1 Introduction 8
1.4.2 OxidationofPhosphines 9
1.4.3 OxidativeAdditionofaP–CBondtoaLow-ValentMetal 11
1.4.4 NucleophilicAttackatPhosphorus 16
1.4.5 ArylExchangeViaPhosphoniumIntermediates 19
1.4.6 ArylExchangeViaMetallophosphoranes 21
1.5 Phosphites 23
1.6 IminesandPyridines 26
1.7 Carbenes 27
1.7.1 IntroductiontoNHCsasLigands 27
1.7.2 ReductiveEliminationofNHCs 28
1.7.3 CarbeneDecompositioninMetathesisCatalysts 31
1.8 ReactionsofMetal–CarbonandMetal–HydrideBonds 36
1.8.1 ReactionswithProticReagents 36
1.8.2 ReactionsofZirconiumandTitaniumAlkylCatalysts 37
1.9 ReactionsBlockingtheActiveSites 38
1.9.1 PolarImpurities 38
1.9.2 DimerFormation 39
VI Contents
1.9.3 LigandMetallation 40
References 41
2 EarlyTransitionMetalCatalystsforOlefinPolymerization 51
2.1 Ziegler–NattaCatalysts 51
2.1.1 Introduction 51
2.1.2 EffectofCatalystPoisons 52
2.1.3 TiCl Catalysts 53
3
2.1.4 MgCl -supportedCatalysts 54
2
2.1.4.1 MgCl /TiCl /EthylBenzoateCatalysts 54
2 4
2.1.4.2 MgCl /TiCl /DiesterCatalysts 56
2 4
2.1.4.3 MgCl /TiCl /DietherCatalysts 57
2 4
2.1.5 EthenePolymerization 57
2.2 Metallocenes 58
2.2.1 Introduction 58
2.2.2 Metallocene/MAOSystems 62
2.2.3 Metallocene/BorateSystems 66
2.3 OtherSingle-CenterCatalysts 69
2.3.1 ConstrainedGeometryandHalf-SandwichComplexes 69
2.3.2 OctahedralComplexes 73
2.3.3 DiamideandOtherComplexes 75
2.4 Vanadium-BasedCatalysts 76
2.5 Chromium-BasedCatalysts 80
2.6 Conclusions 82
References 83
3 LateTransitionMetalCatalystsforOlefinPolymerization 91
3.1 Nickel-andPalladium-basedCatalysts 91
3.1.1 DiimineComplexes 91
3.1.2 NeutralNickel(II)Complexes 94
3.1.3 OtherNickel(II)andPalladium(II)Complexes 98
3.2 Iron-andCobalt-basedCatalysts 98
3.2.1 Bis(imino)PyridylComplexes 98
3.3 Conclusions 101
References 102
4 EffectsofImmobilizationofCatalystsforOlefin
Polymerization 105
4.1 Introduction 105
4.2 MetallocenesandRelatedComplexes 106
4.2.1 ImmobilizedMAO/MetalloceneSystems 106
4.2.2 ImmobilizedBoraneandBorateActivators 109
4.2.3 SuperacidicSupports 110
4.2.4 MgCl -SupportedSystems 110
2
4.3 OtherTitaniumandZirconiumComplexes 113
Contents VII
4.3.1 ConstrainedGeometryComplexes 113
4.3.2 OctahedralComplexes 115
4.4 VanadiumComplexes 117
4.5 ChromiumComplexes 121
4.6 NickelComplexes 122
4.7 IronComplexes 124
4.8 Conclusions 125
References 126
5 DormantSpeciesinTransitionMetal-Catalyzed
OlefinPolymerization 131
5.1 Introduction 131
5.2 Ziegler–NattaCatalysts 132
5.2.1 EthenePolymerization 132
5.2.2 PropenePolymerization 132
5.3 MetallocenesandRelatedEarlyTransitionMetal
Catalysts 134
5.3.1 Cation–AnionInteractions 134
5.3.2 EffectsofAlMe 136
3
5.3.3 Effectsof2,1-insertioninPropenePolymerization 137
5.3.4 EffectsofZ3-allylicSpeciesinPropenePolymerization 140
5.3.5 ChainEpimerizationinPropenePolymerization 141
5.3.6 EffectsofDormantSiteFormationonPolymerization
Kinetics 142
5.4 LateTransitionMetalCatalysts 143
5.4.1 RestingStatesinNickelDiimine-Catalyzed
Polymerization 143
5.4.2 EffectsofHydrogeninBis(iminopyridyl)Iron-Catalyzed
Polymerization 143
5.5 ReversibleChainTransferinOlefinPolymerization 145
5.6 Conclusions 147
References 148
6 TransitionMetalCatalyzedOlefinOligomerization 151
6.1 Introduction 151
6.2 ZirconiumCatalysts 152
6.3 TitaniumCatalysts 153
6.4 TantalumCatalysts 156
6.5 ChromiumCatalysts 157
6.5.1 Chromium-catalyzedTrimerization 157
6.5.2 Chromium-catalyzedTetramerizationofEthene 160
6.5.3 Chromium-CatalyzedOligomerization 162
6.5.4 Single-componentChromiumCatalysts 164
6.6 NickelCatalysts 166
6.7 IronCatalysts 168
VIII Contents
6.8 TandemCatalysisinvolvingOligomerizationand
Polymerization 170
6.9 Conclusions 171
References 172
7 AsymmetricHydrogenation 177
7.1 Introduction 177
7.2 IncubationbyDienesinRhodiumDiene
Precursors 179
7.3 InhibitionbySubstrates,Solvents,PolarAdditives,
andImpurities 181
7.3.1 InhibitionbySubstrates:Iridium 181
7.3.2 InhibitionbySubstrates,Additives:Rhodium 182
7.3.3 InhibitionbySubstrates:Ruthenium 187
7.4 InhibitionbyFormationofBridgedSpecies 190
7.4.1 InhibitionbyFormationofBridgedSpecies:
Iridium 191
7.4.2 InhibitionbyFormationofBridgedSpecies:
Rhodium 195
7.5 InhibitionbyLigandDecomposition 198
7.6 InhibitionbytheProduct 199
7.6.1 InhibitionbytheProduct:Rhodium 199
7.6.2 Ruthenium 200
7.7 InhibitionbyMetalFormation;Heterogeneous
CatalysisbyMetals 201
7.8 SelectiveActivationandDeactivationofEnantiomeric
Catalysts 204
7.9 Conclusions 206
References 207
8 CarbonylationReactions 213
8.1 Introduction 213
8.2 Cobalt-CatalyzedHydroformylation 214
8.3 Rhodium-CatalyzedHydroformylation 217
8.3.1 IntroductionofRhodium-CatalyzedHydroformylation 217
8.3.2 CatalystFormation 221
8.3.3 IncubationbyImpurities:DormantSites 223
8.3.4 DecompositionofPhosphines 227
8.3.5 DecompositionofPhosphites 231
8.3.6 DecompositionofNHCs 235
8.3.7 Two-PhaseHydroformylation 238
8.3.8 HydroformylationbyNanoparticlePrecursors 244
8.4 Palladium-CatalyzedAlkene–COReactions 244
8.4.1 Introduction 244
8.4.2 BriefMechanisticOverview 246
Contents IX
8.4.3 EarlyReportsonDecompositionandReactivation 248
8.4.4 Copolymerization 250
8.4.5 Methoxy-andHydroxy-carbonylation 253
8.5 MethanolCarbonylation 259
8.5.1 Introduction 259
8.5.2 MechanismandSideReactionsoftheMonsanto
Rhodium-BasedProcess 260
8.5.3 TheMechanismoftheAceticAnhydrideProcessUsing
RhodiumasaCatalyst 261
8.5.4 Phosphine-ModifiedRhodiumCatalysts 263
8.5.5 IridiumCatalysts 265
8.6 Conclusions 268
References 269
9 Metal-CatalyzedCross-CouplingReactions 279
9.1 Introduction;AFewHistoricNotes 279
9.2 OntheMechanismofInitiationandPrecursors 283
9.2.1 InitiationviaOxidativeAdditiontoPd(0) 283
9.2.2 HydrocarbylPdHalideInitiators 290
9.2.3 MetallatedHydrocarbylPdHalideInitiators 293
9.3 Transmetallation 299
9.4 ReductiveElimination 303
9.4.1 MonodentatevsBidentatePhosphinesandReductive
Elimination 303
9.4.2 ReductiveEliminationofC–FBonds 313
9.5 PhosphineDecomposition 316
9.5.1 PhosphineOxidation 316
9.5.2 P–CCleavageofLigands 317
9.6 MetalImpurities 322
9.7 MetalNanoparticlesandSupportedMetal
Catalysts 327
9.7.1 SupportedMetalCatalysts 327
9.7.2 MetalNanoparticlesasCatalysts 330
9.7.3 MetalPrecipitation 334
9.8 Conclusions 334
References 335
10 AlkeneMetathesis 347
10.1 Introduction 347
10.2 MolybdenumandTungstenCatalysts 349
10.2.1 DecompositionRoutesofAlkeneMetathesisCatalysts 349
10.2.2 RegenerationofActiveAlkylidenesSpecies 356
10.2.3 DecompositionRoutesofAlkyneMetathesisCatalysts 359
10.3 RheniumCatalysts 363
10.3.1 Introduction 363
X Contents
10.3.2 CatalystInitiationandDecomposition 365
10.4 RutheniumCatalysts 370
10.4.1 Introduction 370
10.4.2 InitiationandIncubationPhenomena 371
10.4.3 DecompositionoftheAlkylideneFragment 376
10.4.4 ReactionsInvolvingtheNHCLigand 379
10.4.5 ReactionsInvolvingOxygenates 381
10.4.6 TandemMetathesis/HydrogenationReactions 385
10.5 Conclusions 388
References 390
Index 397