Homogeneous Catalysis: Understanding the Art

摘要: Preface.- Acknowledgements.- 1: Introduction.- 1.1. Catalysis. 1.2. Homogeneous catalysis. 1.3. Historical notes on homogeneous 1.4. Characterization of the catalyst. 1.5. Ligand effects. 1.6. Ligands according to donor atoms. 2: Elementary Steps.- 2.1. Creation a 'vacant' site and co-ordination substrate. 2.2. Insertion versus migration. 2.3. beta-Elimination de-insertion. 2.4. Oxidative addition. 2.5. Reductive elimination. 2.6. alpha-Elimination reactions. 2.7. Cycloaddition reactions involving metal. 2.8. Activation substrate toward nucleophilic attack. 2.9. sigma-Bond metathesis. 2.10. Dihydrogen activation. 2.11. by Lewis acids. 2.12. Carbon-to-phosphorus bond breaking. 2.13. Carbon-to-sulfur 2.14. Radical 3: Kinetics.- 3.1. Introduction. 3.2. Two-step reaction scheme. 3.3. Simplifications rate equation rete-determining step. 3.4. Determining selectivity. 3.5. Collection data. 3.6. Irregularities in 4: Hydrogenation.- 4.1. Wilkinson's 4.2. Asymmetric hydrogenation. 4.3. Overview chiral bidentate ligands. 4.4. Monodentate 4.5. Non-linear 4.6. Hydrogen transfer. 5: Isomerisation.- 5.1. shifts. 5.2. isomerisation. 5.3. Oxygen 6: Carbonylation Methanol Methyl Acetate.- 6.1. Acetic acid. 6.2. Process scheme Monsanto process. 6.3. anhydride. 6.4. Other systems. 7: Cobalt Catalysed Hydroformylation.- 7.1. 7.2. Thermodynamics. 7.3. catalysed processes. 7.4. processes for higher alkenes. 7.5. Kuhlmann cobalt hydroformylation 7.6. Phosphine modified catalysts: shell 7.7. carbonyl phosphine complexes. 8: Rhodium 8.1. 8.2. Triphenylphosphine asthe ligand. 8.3. Diphosphines as 8.4. Phosphites 8.5. Diphosphites. 8.6. hydroformylation. 9: Alkene Oligomerisation.- 9.1. 9.2. Shell-higher-olefins-process. 9.3. Ethene trimerisation. 9.4. alkene oligomerisation 10: Propene Polymerisation.- 10.1. Introduction polymer chemistry. 10.2. Mechanistic investigations. 10.3. Analysis 13CNMR spectroscopy. 10.4. The development metallocene catalysts. 10.5. Agostic interactions. 10.6. effect dihydrogen. 10.7. Further work using propene other 10.8. Non-metallocene ETM 10.9. Late transition metal 11: Hydrocyanation Alkenes.- 11.1. adiponitrile 11.2. 12: Palladium Carbonylations 12.1. 12.2. Polyketone. 12.3. effects chain length. 12.4. Ethene/propene/CO terpolymers. 12.5. Stereoselective styrene/CO 13: Cross-Coupling Reactions.- 13.1. 13.2. Allylic reaction. 13.3. Heck 13.4. Cross-coupling 13.5. Heteroatom-carbon formation. 13.6. Suzuki 14: Epoxidation.- 14.1. oxide. 14.2. epoxidation. 14.3. hydroxilation alkenes with osmium tetroxide. 14.4. Jacobsen asymmetric ring-opening epoxides. 14.5. Epoxidations dioxygen. 15: Oxydation Dioxygen.- 15.1. 15.2. Wacker 15.3. type 15.4. Terephthalic 15.5. PPO. 16: Metathesis.- 16.1. 16.2. mechanism. 16.3. Reaction overview. 16.4. Well-characterised tungsten molybdenum 16.5. Ruthenium 16.6. Stereochemistry. 16.7. Catalyst decomposition. 16.8. Alkynes. 16.9. Industrial applications. 17: Enantioselective Cyclopropanation.-