Homogeneous Catalysis: Understanding the Art

Preface.- Acknowledgements.- 1: Introduction.- 1.1. Catalysis. 1.2. Homogeneous catalysis. 1.3. Historical notes on homogeneous catalysis. 1.4. Characterization of the catalyst. 1.5. Ligand effects. 1.6. Ligands according to donor atoms. 2: Elementary Steps.- 2.1. Creation of a 'vacant' site and co-ordination of the substrate. 2.2. Insertion versus migration. 2.3. beta-Elimination and de-insertion. 2.4. Oxidative addition. 2.5. Reductive elimination. 2.6. alpha-Elimination reactions. 2.7. Cycloaddition reactions involving a metal. 2.8. Activation of a substrate toward nucleophilic attack. 2.9. sigma-Bond metathesis. 2.10. Dihydrogen activation. 2.11. Activation by Lewis acids. 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 rete-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. 4.3. Overview of chiral bidentate 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. 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. 8: Rhodium Catalysed Hydroformylation.- 8.1. Introduction. 8.2. Triphenylphosphine asthe ligand. 8.3. Diphosphines as ligands. 8.4. Phosphites as ligands. 8.5. Diphosphites. 8.6. Asymmetric hydroformylation. 9: Alkene Oligomerisation.- 9.1. Introduction. 9.2. Shell-higher-olefins-process. 9.3. Ethene trimerisation. 9.4. Other alkene oligomerisation reactions. 10: Propene Polymerisation.- 10.1. Introduction to polymer chemistry. 10.2. Mechanistic investigations. 10.3. Analysis by 13CNMR spectroscopy. 10.4. The development of metallocene catalysts. 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. 12.3. Ligand effects on chain length. 12.4. Ethene/propene/CO terpolymers. 12.5. Stereoselective styrene/CO terpolymers. 13: Palladium Catalysed Cross-Coupling Reactions.- 13.1. Introduction. 13.2. Allylic reaction. 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. 14.3. Asymmetric hydroxilation of alkenes with osmium tetroxide. 14.4. Jacobsen asymmetric ring-opening of epoxides. 14.5. Epoxidations with dioxygen. 15: Oxydation 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.-