过渡金属化合物均相催化领城近年来发展非常迅速，工业界、学术界纷纷报道发现了众多的奇妙催化剂。本书基于作者在教学及工业实践方面广泛的经验，探讨了许多新的和旧的重要反应。每章均以基础知识开始，以最新的内容结束。本书侧重于概念，但也列举了许多实验室合成有机化学品的关键丁业流程和应用流程。全书涵盖精细化学品，大宗化学品，聚合物，高技术聚合物，药品，也包括重要的技巧和反应类型等。同时还介绍了一些反应过程方案、环境问题和安全问题。

本书可供催化专业高年级本科生、研究生以及研究人员参考使用。

Preface

Acknowledgements

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 a-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 RATEDETERMINING 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/Rhone-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 BY13C 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 WACKIER REACTION

 15.3 WACKIER 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 a-BOND METATHESIS

 19.7 ELECTROPHILIC CATALYSTS

SUBJECT INDEX