Supported Metal Complexes: A New Generation of Catalysts

1. Introduction. - 1.1. Catalysis. - 1.2. Reasons for Supporting Metal Complexes. - 1.3. Catalyst Requirements. - 1.4. Types of Support. - 1.4.1. Organic Polymers. - 1.4.2. Inorganic Supports. - 1.5. Chemically Modified Electrodes. - 1.6. Immobilised Enzymes and Reagents for Organic Syntheses. - 1.7. Triphase Catalysis. - 1.8. Heterogenisation of Metal Complex Catalysts. - 1.8.1. Phase Transfer. - 1.8.2. Supported Liquid and Gas Phase Catalysts. - 1.8.3. Use of Melts. - 1.8.4. Lattice Metal Complexes. - 1.8.5. Water Soluble Complexes. - 1.9. Polymer Supported Metal Catalysts. - References. - 2. Preparation of the Supports. - 2.1. General Considerations for Organic Polymers. - 2.2. Styrene Based Systems. - 2.2.1. Functionalisation of Preformed Polystyrene. - 2.2.2. Copolymerisation of Functionalised Styrenes. - 2.3. Non-Styrene Polymers. - 2.4. Radiation Grafting. - 2.4.1. Techniques of Radiation Grafting. - 2.4.2. Reactions Occurring under the Influence of Radiation. - 2.4.3. Factors Affecting Radiation Grafting. - 2.5. Silica-Based Systems. - 2.6. Other Inorganic Supports. - References. - 3. Introduction of Metals onto Supports. - 3.1. Ion-Exchange-Based Catalysts. - 3.2. Functionalised Supports. - 3.3. Metal Complexes Bound to Polymeric Supports Through Metal-Carbon Bonds. - 3.4. Polymerisation of Functionalised Monomers. - 3.5. Direct Reaction Between Organometallic Compounds and Inorganic Oxide Surfaces. - 3.6. Surface Bonding of Metal Carbonyls on Inorganic Oxides. - 3.7. Supported Ziegler-Natta Catalysts. - 3.8. Surface Supported Metal Salts. - 3.9. Surface Complexes of Transition Metal Oxides on Oxide Supports. - References. - 4. Characterisation of Supported Catalysts. - 4.1. Microanalysis. - 4.2. Chromatographic Methods. - 4.2.1. Gel Chromatography. - 4.2.2. Temperature Programmed Decomposition Chromatography. - 4.3. Spectroscopic Methods. - 4.3.1 Infrared. - 4.3.2 Raman. - 4.3.3 Inelastic Electron Tunnelling. - 4.3.4. Ultraviolet and Visible. - 4.3.5. Nuclear Magnetic Resonance. - 4.3.6. Electron Spin Resonance. - 4.3.7. Moessbauer. - 4.3.8. Mass Spectrometry. - 4.3.9. ESCA. - 4.3.10. Extended X-ray Absorption Fine Structure. - 4.4. Electron Microscopy. - References. - 5. The Use of Supported Metal Complex Catalysts. - 5.1. Introduction. - 5.2. Optimisation of Conditions. - 5.3. Laboratory Application. - 5.4. Industrial Application. - References. - 6. Hydrogenation. - 6.1. Introduction. - 6.2. Nature of the Support. - 6.3. Effect of Cross-Linking. - 6.4. Nature of the Solvent. - 6.5. Nature of the Metal Complex. - 6.6. Activity of Supported as Compared to Homogeneous Catalysts. - 6.7. Selectivity. - 6.8. Stability. - 6.9. Survey of Supported Hydrogenation Catalysts. - 6.9.1. Titanium, Zirconium and Hafnium. - 6.9.2. Chromium, Molybdenum and Tungsten. - 6.9.3. Iron, Ruthenium and Osmium. - 6.9.4. Cobalt. - 6.9.5. Rhodium. - 6.9.5.1. Analogues of [Rh(PPh3)3Cl]. - 6.9.5.2. Other Rhodium(I)-Phosphine Complexes. - 6.9.5.3. Rhodium(I)-Phosphinite Complexes. - 6.9.5.4. Rhodium Carbonyl Complexes. - 6.9.5.5. Organometallic Rhodium Complexes. - 6.9.5.6. Rhodium Carboxylate Complexes. - 6.9.5.7. Rhodium Amide and Imidazole Complexes. - 6.9.5.8. Rhodium Thioether Complexes. - 6.9.5.9. Organorhodium(III) Complexes. - 6.9.6. Asymmetric Hydrogenation. - 6.9.7. Iridium. - 6.9.8. Nickel. - 6.9.9. Palladium and Platinum. - 6.9.10. Actinides. - 6.10. Reduction of Inorganic Molecules. - 6.11. Michael Addition. - References. - 7. Hydrosilylation. - 8. Reactions Involving Carbon Monoxide. - 8.1. Introduction. - 8.2. Hydroformylation. - 8.2.1. Cobalt Hydroformylation Catalysts. - 8.2.2. Rhodium(I) Hydroformylation Catalysts. - 8.2.3. Asymmetric Hydroformylation. - 8.2.4. Other Transition Metal Hydroformylation Catalysts. - 8.3. Carbonylation of Methanol. - 8.4. Fischer-Tropsch Reaction. - 8.4.1. Fischer-Tropsch Formation of Paraffins. - 8.4.2. Fischer-Tropsch Formation of Olefins. - 8.4.3. Fischer-Tropsch Formation of Alcohols. - 8.5. Water Gas Shift Reaction. - 8.6. Alkoxycarbonylation of Olefins. - 8.7. Isocyanates Formed by Carbonylation of Nitro Compounds and Azides. - 8.8. Syntheses of Aldehydes and Ketones. - 8.9. Substitution of Carbonyl Ligands in Metal Carbonyls. - References. - 9. Dimerisation, Oligomerisation, Polymerisation, Disproportionation and Isomerisation. - 9.1. Olefin Dimerisation. - 9.2. Olefin Trimerisation. - 9.3. Oligomerisation and Cyclooligomerisation of Dienes. - 9.4. Oligomerisation of Acetylenes. - 9.5. Polymerisation of Olefins. - 9.5.1. Inorganic Oxide Supported Olefin Polymerisation Catalysts. - 9.5.2. Polymer Supported Olefin Polymerisation Catalysts. - 9.6. Diene Polymerisation. - 9.7. Acetylene Polymerisation. - 9.8. Copolymerisation of Propylene Oxide with Carbon Dioxide. - 9.9. Olefin Metathesis. - 9.10. Olefin Isomerisation. - 9.10.1. Zirconium Complexes. - 9.10.2. Iron, Ruthenium and Osmium Carbonyl Complexes. - 9.10.3. Ruthenium(II) and Rhodium(l) Carbonyl and Carboxylate Complexes. - 9.10.4. Silica Supported Rhodium Catalysts. - 9.10.5. Nickel Catalysts. - 9.10.6. Palladium Catalysts. - 9.11. Quadricyclane-Norbornadiene Isomerisation. - 9.11.1. Quadricyclane to Norbornadiene Isomerisation. - 9.11.2. Norbornadiene to Quadricyclane Isomerisation. - 9.12. Grignard Cross-Coupling Reactions. - References. - 10. Oxidation and Hydrolysis. - 10.1. Hydrocarbon Oxidation. - 10.2. Decomposition of Peroxides. - 10.3. Oxidation of Organic Compounds. - 10.4. Oxidation of Inorganic Compounds. - 10.5. Chlorination. - 10.6. Ammoxidation. - 10.7. Hydroxylation of Aromatic Compounds. - 10.8. Hydroxylation of Olefins. - 10.9. Carboxylation of Olefins and Aromatic Compounds. - 10.10. Vinyl Ester and Ether Exchange. - 10.11. Nitrile Hydrolysis. - 10.12. Nucleophilic Substitution of Acetate Groups. - 10.13. Stereoselective Hydrolysis of Esters. - References. - 11. Conclusions And Future Possibilities. - 11.1. Sequential Multistep Reactions. - 11.2. Selectivity Enhancement. - 11.3. Activity. - 11.4. Organic versus Inorganic Supports. - 11.5 Future Developments. - References.