1．INTRODUCTION

1.1 CATALYSIS

1.2 HOMOGENEOUS CATALYSIS

1.3 HISTORICAL NOTES ON HOMOGENEOUS CATALYSIS

1.4 CHARACTERISATION OF THE CATALYST

1.5 LIGAND EFFECTS

1.5.1 Phosphines and phosphites:electronic effects

1.5.2 Phosphines and phosphites:steric effects

1.5.3 Linear Free Energy Relationships

1.5.4 Phosphines and phosphites:bite angle effects

1.6 LIGANDS ACCORDING TO DONOR ATOMS

1.6.1 Anionic and neutral hydrocarbyl groups

1.6.2 Alkoxy and imido groups as anionic ligands

1.6.3 Amines,imines,oxazolines and related ligands

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

1.6.5 Carbenes,carbon monoxide

1.6.6 Common anions

2．ELEMENTARY STEPS

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

2.2 INSERTION VERSUS MIGRATION

2.3 β-ELIMINATION AND DE-INSERTION

2.4 OXIDATIVE ADDITION

2.5 REDUCTIVE ELIMINATION

2.6 α-ELIMINATION REACTIONS

2.7 CYCLOADDITION REACTIONS INVOLVING A METAL

2.8 ACTIVATION OF A SUBSTRATE TOWARD NUCLEOPHILIC ATTACK

2.8.1 Alkenes

2.8.2 Alkynes

2.8.3 Carbon monoxide

2.8.4 Other substrates

2.9 σ-BOND METATHESIS

2.10 DIHYDROGEN ACTIVATION

2.11 ACTIVATION BY LEWIS ACIDS

2.11.1 Diels-Alder additions

2.11.2 Epoxidation

2.11.3 Ester condensation

2.12 CARBON-TO-PHOSPHORUS BOND BREAKING

2.13 CARBON-TO-SULFUR BOND BREAKING

2.14 RADICAL REACTIONS

3．KINETICS

3.1 INTRODUCTION

3.2 TWO-STEP REACTION SCHEME

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

3.4 DETERMINING THE SELECTIVITY

3.5 COLLECTION OF RATE DATA

3.6 IRREGULARITIES IN CATALYSIS

4．HYDROGENATION

4.1 WILKINSON'S CATALYST

4.2 ASYMMETRIC HYDROGENATION

4.2.1 Introduction

4.2.2 Cinnamic acid derivatives

4.2.3 Chloride versus weakly coordinating anions;alkylphosphines versus arylphosphines

4.2.4 Incubation times

4.3 OVERVIEW OF CHIRAL BIDENTATE LIGANDS

4.3.1 DuPHOS

4.3.2 BINAP catalysis

4.3.3 Chiral ferrocene based ligands

4.4 MONODENTATE LIGANDS

4.5 NON-LINEAR EFFECTS

4.6 HYDROGEN TRANSFER

5．ISOMERISATION

5.1 HYDROGEN SHIFTS

5.2 ASYMMETRIC ISOMERISATION

5.3 OXYGEN SHIFTS

6．CARBONYLATION OF METHANOL AND METHYL ACETATE

6.1 ACETIC ACID

6.2 PROCESS SCHEME MONSANTO PROCESS

6.3 ACETIC ANHYDRIDE

6.4 OTHER SYSTEMS

6.4.1 Higher alcohols

6.4.2 Phosphine-modified rhodium catalysts

6.4.3 Other metals

7．COBALT CATALYSED HYDROFORMYLATION

7.1 INTRODUCTION

7.2 THERMODYNAMICS

7.3 COBALT CATALYSED PROCESSES

7.4 COBALT CATALYSED PROCESSES FOR HIGHER ALKENES

7.5 KUHLMANN COBALT HYDROFORMYLATION PROCESS

7.6 PHOSPHINE MODIFIED COBALT CATALYSTS:THE SHELL PROCESS

7.7 COBALT CARBONYL PHOSPHINE COMPLEXES

7.7.1 Carbonyl species

7.7.2 Phosphine derivatives

8．RHODIUM CATALYSED HYDROFORMYLATION

8.1 INTRODUCTION

8.2 TRIPHENYLPHOSPHINE AS THE LIGAND

8.2.1 The mechanism

8.2.2 Ligand effects and kinetics

8.2.3 Regioselectivity

8.2.4 Process description,rhodium-tpp

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

8.2.6 One-phase catalysis,two-phase separation

8.3 DIPHOSPHINES AS LIGANDS

8.3.1 Xantphos ligands:tuneable bite angles

8.4 PHOSPHITES AS LIGANDS

8.4.1 Electronic effects

8.4.2 Phosphites:steric effects

8.5 DIPHOSPHITES

8.6 ASYMMETRIC HYDROFORMYLATION

8.6.1 Rhodium catalysts:diphosphites

8.6.2 Rhodium catalysts:phosphine-phosphite ligands

9．ALKENE OLIGOMERISATION

9.1 INTRODUCTION

9.2 SHELL-HIGHER-OLEFINS-PROCESS

9.2.1 Oligomerisation

9.2.2 Separation

9.2.3 Purification,isomerisation,and metathesis

9.2.4 New catalysts

9.3 ETHENE TRIMERISATION

9.4 OTHER ALKENE OLIGOMERISATION REACTIONS

10．PROPENE POLYMERISATION

10.1 INTRODUCTION TO POLYMER CHEMISTRY

10.1.1 Introduction to Ziegler Natta polymerisation

10.1.2 History of homogeneous catalysts

10.2 MECHANISTIC INVESTIGATIONS

10.2.1 Chain-end control:syndiotactic polymers

10.2.2 Chain-end control:isotactic polymers

10.3 ANALYSIS BY 13 C NMR SPECTROSCOPY

10.3.1 Introduction

10.3.2 Chain-end control

10.3.3 Site control mechanism

10.4 THE DEVELOPMENT OF METALLOCENE CATALYSTS

10.4.1 Site control:isotactic polymers

10.4.2 Site control:syndiotactic polymers

10.4.3 Double stereoselection:chain-end and site control

10.5 AGOSTIC INTERACTIONS

10.6 THE EFFECT OF DIHYDROGEN

10.7 FURTHER WORK USING PROPENE AND OTHER ALKENES

10.8 NON-METALLOCENE ETM CATALYSTS

10.9 LATE TRANSITION METAL CATALYSTS

11．HYDROCYANATION OF ALKENES

11.1 THE ADIPONITRILE PROCESS

11.2 LIGAND EFFECTS

12．PALLADIUM CATALYSED CARBONYLATIONS OF ALKENES

12.1 INTRODUCTION

12.2 POLYKETONE

12.2.1 Background and history

12.2.2 Elementary steps:initiation

12.2.3 Elementary steps:migration reactions

12.2.4 Elementary steps:chain termination,chain transfer

12.2.5 Elementary steps:ester formation as chain termination

12.3 LIGAND EFFECTS ON CHAIN LENGTH

12.3.1 Polymers

12.3.2 Ligand effects on chain length:Propanoate

12.3.3 Ligand effects on chain length:Oligomers

12.4 ETHENE/PROPENE/CO TERPOLYMERS

12.5 STEREOSELECTIVE STYRENE/CO COPOLYMERS

13．PALLADIUM CATALYSED CROSS-COUPLING REACTIONS

13.1 INTRODUCTION

13.2 ALLYLIC ALKYLATION

13.3 HECK REACTION

13.4 CROSS-COUPLING REACTION

13.5 HETEROATOM-CARBON BOND FORMATION

13.6 SUZUKI REACTION

14．EPOXIDATION

14.1 ETHENE AND PROPENE OXIDE

14.2 ASYMMETRIC EPOXIDATION

14.2.1 Introduction

14.2.2 Katsuki-Sharpless asymmetric epoxidation

14.2.3 The Jacobsen asymmetric epoxidation

14.3 ASYMMETRIC HYDROXYLATION OF ALKENES WITH OSMIUM TETROXIDE

14.3.1 Stoichiometric reactions

14.3.2 Catalytic reactions

14.4 JACOBSEN ASYMMETRIC RING-OPENING OF EPOXIDES

14.5 EPOXIDATIONS WITH DIOXYGEN

15．OXIDATION WITH DIOXYGEN

15.1 INTRODUCTION

15.2 THE WACKER REACTION

15.3 WACKER TYPE REACTIONS

15.4 TEREPHTHALIC ACID

15.5 PPO

16．ALKENE METATHESIS

16.1 INTRODUCTION

16.2 THE MECHANISM

16.3 REACTION OVERVIEW

16.4 WELL-CHARACTERISED TUNGSTEN AND MOLYBDENUM CATALYSTS

16.5 RUTHENIUM CATALYSTS

16.6 STEREOCHEMISTRY

16.7 CATALYST DECOMPOSITION

16.8 ALKYNES

16.9 INDUSTRIAL APPLICATIONS

17．ENANTIOSELECTIVE CYCLOPROPANATION

17.1 INTRODUCTION

17.2 COPPER CATALYSTS

17.3 RHODIUM CATALYSTS

17.3.1 Introduction

17.3.2 Examples of rhodium catalysts

18．HYDROSILYLATION

18.1 INTRODUCTION

18.2 PLATINUM CATALYSTS

18.3 ASYMMETRIC PALLADIUM CATALYSTS

18.4 RHODIUM CATALYSTS FOR ASYMMETRIC KETONE REDUCTION

19．C-H FUNCTIONALISATION

19.1 INTRODUCTION

19.2 ELECTRON-RICH METALS

19.3 HYDROGEN TRANSFER REACTIONS OF ALKANES

19.4 BORYLATION OF ALKANES

19.5 THE MURAI REACTION

19.6 CATALYTIC σ-BOND METATHESIS

19.7 ELECTROPHILIC CATALYSTS

SUBJECT INDEX