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1．INTRODUCTION1

1.1 CATALYSIS1

1.2 HOMOGENEOUS CATALYSIS6

1.3 HISTORICAL NOTES ON HOMOGENEOUS CATALYSIS7

1.4 CHARACTERISATION OF THE CATALYST8

1.5 LIGAND EFFECTS10

1.5.1 Phosphines and phosphites:electronic effects10

1.5.2 Phosphines and phosphites:steric effects12

1.5.3 Linear Free Energy Relationships14

1.5.4 Phosphines and phosphites:bite angle effects16

1.6 LIGANDS ACCORDING TO DONOR ATOMS20

1.6.1 Anionic and neutral hydrocarbyl groups20

1.6.2 Alkoxy and imido groups as anionic ligands21

1.6.3 Amines,imines,oxazolines and related ligands21

1.6.4 Phosphines,phosphites,phosphorus amides,phospholes and related ligands23

1.6.5 Carbenes,carbon monoxide24

1.6.6 Common anions25

2．ELEMENTARY STEPS29

2.1 CREATION OF A"VACANT"SITE AND CO-ORDINATION OF THE SUBSTRATE29

2.2 INSERTION VERSUS MIGRATION30

2.3 β-ELIMINATION AND DE-INSERTION35

2.4 OXIDATIVE ADDITION36

2.5 REDUCTIVE ELIMINATION39

2.6 α-ELIMINATION REACTIONS41

2.7 CYCLOADDITION REACTIONS INVOLVING A METAL42

2.8 ACTIVATION OF A SUBSTRATE TOWARD NUCLEOPHILIC ATTACK44

2.8.1 Alkenes44

2.8.2 Alkynes45

2.8.3 Carbon monoxide45

2.8.4 Other substrates46

2.9 σ-BOND METATHESIS48

2.10 DIHYDROGEN ACTIVATION48

2.11 ACTIVATION BY LEWIS ACIDS50

2.11.1 Diels-Alder additions51

2.11.2 Epoxidation51

2.11.3 Ester condensation52

2.12 CARBON-TO-PHOSPHORUS BOND BREAKING52

2.13 CARBON-TO-SULFUR BOND BREAKING55

2.14 RADICAL REACTIONS57

3．KINETICS63

3.1 INTRODUCTION63

3.2 TWO-STEP REACTION SCHEME63

3.3 SIMPLIFICATIONS OF THE RATE EQUATION AND THE RATE-DETERMINING STEP64

3.4 DETERMINING THE SELECTIVITY68

3.5 COLLECTION OF RATE DATA71

3.6 IRREGULARITIES IN CATALYSIS72

4．HYDROGENATION75

4.1 WILKINSON'S CATALYST75

4.2 ASYMMETRIC HYDROGENATION77

4.2.1 Introduction77

4.2.2 Cinnamic acid derivatives79

4.2.3 Chloride versus weakly coordinating anions;alkylphosphines versus arylphosphines86

4.2.4 Incubation times86

4.3 OVERVIEW OF CHIRAL BIDENTATE LIGANDS86

4.3.1 DuPHOS86

4.3.2 BINAP catalysis87

4.3.3 Chiral ferrocene based ligands89

4.4 MONODENTATE LIGANDS90

4.5 NON-LINEAR EFFECTS93

4.6 HYDROGEN TRANSFER94

5．ISOMERISATION101

5.1 HYDROGEN SHIFTS101

5.2 ASYMMETRIC ISOMERISATION103

5.3 OXYGEN SHIFTS105

6．CARBONYLATION OF METHANOL AND METHYL ACETATE109

6.1 ACETIC ACID109

6.2 PROCESS SCHEME MONSANTO PROCESS114

6.3 ACETIC ANHYDRIDE116

6.4 OTHER SYSTEMS118

6.4.1 Higher alcohols118

6.4.2 Phosphine-modified rhodium catalysts119

6.4.3 Other metals122

7．COBALT CATALYSED HYDROFORMYLATION125

7.1 INTRODUCTION125

7.2 THERMODYNAMICS126

7.3 COBALT CATALYSED PROCESSES126

7.4 COBALT CATALYSED PROCESSES FOR HIGHER ALKENES128

7.5 KUHLMANN COBALT HYDROFORMYLATION PROCESS130

7.6 PHOSPHINE MODIFIED COBALT CATALYSTS:THE SHELL PROCESS131

7.7 COBALT CARBONYL PHOSPHINE COMPLEXES132

7.7.1 Carbonyl species132

7.7.2 Phosphine derivatives135

8．RHODIUM CATALYSED HYDROFORMYLATION139

8.1 INTRODUCTION139

8.2 TRIPHENYLPHOSPHINE AS THE LIGAND141

8.2.1 The mechanism141

8.2.2 Ligand effects and kinetics144

8.2.3 Regioselectivity147

8.2.4 Process description,rhodium-tpp149

8.2.5 Two-phase process,tppts:Ruhrchemie/Rh？ne-Poulenc150

8.2.6 One-phase catalysis,two-phase separation152

8.3 DIPHOSPHINES AS LIGANDS153

8.3.1 Xantphos ligands:tuneable bite angles155

8.4 PHOSPHITES AS LIGANDS161

8.4.1 Electronic effects161

8.4.2 Phosphites:steric effects162

8.5 DIPHOSPHITES163

8.6 ASYMMETRIC HYDROFORMYLATION166

8.6.1 Rhodium catalysts:diphosphites166

8.6.2 Rhodium catalysts:phosphine-phosphite ligands168

9．ALKENE OLIGOMERISATION175

9.1 INTRODUCTION175

9.2 SHELL-HIGHER-OLEFINS-PROCESS176

9.2.1 Oligomerisation176

9.2.2 Separation180

9.2.3 Purification,isomerisation,and metathesis180

9.2.4 New catalysts181

9.3 ETHENE TRIMERISATION184

9.4 OTHER ALKENE OLIGOMERISATION REACTIONS187

10．PROPENE POLYMERISATION191

10.1 INTRODUCTION TO POLYMER CHEMISTRY191

10.1.1 Introduction to Ziegler Natta polymerisation193

10.1.2 History of homogeneous catalysts196

10.2 MECHANISTIC INVESTIGATIONS199

10.2.1 Chain-end control:syndiotactic polymers199

10.2.2 Chain-end control:isotactic polymers201

10.3 ANALYSIS BY 13 C NMR SPECTROSCOPY202

10.3.1 Introduction202

10.3.2 Chain-end control204

10.3.3 Site control mechanism204

10.4 THE DEVELOPMENT OF METALLOCENE CATALYSTS206

10.4.1 Site control:isotactic polymers206

10.4.2 Site control:syndiotactic polymers209

10.4.3 Double stereoselection:chain-end and site control211

10.5 AGOSTIC INTERACTIONS212

10.6 THE EFFECT OF DIHYDROGEN214

10.7 FURTHER WORK USING PROPENE AND OTHER ALKENES215

10.8 NON-METALLOCENE ETM CATALYSTS220

10.9 LATE TRANSITION METAL CATALYSTS222

11．HYDROCYANATION OF ALKENES229

11.1 THE ADIPONITRILE PROCESS229

11.2 LIGAND EFFECTS233

12．PALLADIUM CATALYSED CARBONYLATIONS OF ALKENES239

12.1 INTRODUCTION239

12.2 POLYKETONE239

12.2.1 Background and history239

12.2.2 Elementary steps:initiation241

12.2.3 Elementary steps:migration reactions244

12.2.4 Elementary steps:chain termination,chain transfer250

12.2.5 Elementary steps:ester formation as chain termination252

12.3 LIGAND EFFECTS ON CHAIN LENGTH256

12.3.1 Polymers256

12.3.2 Ligand effects on chain length:Propanoate258

12.3.3 Ligand effects on chain length:Oligomers261

12.4 ETHENE/PROPENE/CO TERPOLYMERS262

12.5 STEREOSELECTIVE STYRENE/CO COPOLYMERS263

13．PALLADIUM CATALYSED CROSS-COUPLING REACTIONS271

13.1 INTRODUCTION271

13.2 ALLYLIC ALKYLATION273

13.3 HECK REACTION281

13.4 CROSS-COUPLING REACTION286

13.5 HETEROATOM-CARBON BOND FORMATION290

13.6 SUZUKI REACTION294

14．EPOXIDATION299

14.1 ETHENE AND PROPENE OXIDE299

14.2 ASYMMETRIC EPOXIDATION301

14.2.1 Introduction301

14.2.2 Katsuki-Sharpless asymmetric epoxidation301

14.2.3 The Jacobsen asymmetric epoxidation305

14.3 ASYMMETRIC HYDROXYLATION OF ALKENES WITH OSMIUM TETROXIDE308

14.3.1 Stoichiometric reactions308

14.3.2 Catalytic reactions312

14.4 JACOBSEN ASYMMETRIC RING-OPENING OF EPOXIDES314

14.5 EPOXIDATIONS WITH DIOXYGEN316

15．OXIDATION WITH DIOXYGEN319

15.1 INTRODUCTION319

15.2 THE WACKER REACTION320

15.3 WACKER TYPE REACTIONS324

15.4 TEREPHTHALIC ACID327

15.5 PPO332

16．ALKENE METATHESIS337

16.1 INTRODUCTION337

16.2 THE MECHANISM339

16.3 REACTION OVERVIEW343

16.4 WELL-CHARACTERISED TUNGSTEN AND MOLYBDENUM CATALYSTS344

16.5 RUTHENIUM CATALYSTS346

16.6 STEREOCHEMISTRY349

16.7 CATALYST DECOMPOSITION350

16.8 ALKYNES352

16.9 INDUSTRIAL APPLICATIONS354

17．ENANTIOSELECTIVE CYCLOPROPANATION359

17.1 INTRODUCTION359

17.2 COPPER CATALYSTS360

17.3 RHODIUM CATALYSTS364

17.3.1 Introduction364

17.3.2 Examples of rhodium catalysts367

18．HYDROSILYLATION371

18.1 INTRODUCTION371

18.2 PLATINUM CATALYSTS373

18.3 ASYMMETRIC PALLADIUM CATALYSTS378

18.4 RHODIUM CATALYSTS FOR ASYMMETRIC KETONE REDUCTION380

19．C-H FUNCTIONALISATION387

19.1 INTRODUCTION387

19.2 ELECTRON-RICH METALS389

19.3 HYDROGEN TRANSFER REACTIONS OF ALKANES394

19.4 BORYLATION OF ALKANES395

19.5 THE MURAI REACTION396

19.6 CATALYTIC σ-BOND METATHESIS397

19.7 ELECTROPHILIC CATALYSTS397

SUBJECT INDEX403