Supported Metal Complexes

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It is now IS years since the first patents in polymer supported metal complex catalysts were taken out. In the early days ion-exchange resins were used to support ionic metal complexes. Soon covalent links were developed, and after an initially slow start there was a period of explosive growth in the mid to late 1970s during which virtually every homogeneous metal complex catalyst ever reported was also studied bound to a support. Both polymers and inorganic oxides were studied as supports, although the great preponderance of workers studied polymeric supports, and of these polystyrene was by far the commonest used. This period served to show that by very careful design polymer-supported metal complex catalysts could have specific advantages over homogeneous metal complex catalysts. However the subject was a complicated one. Merely immobilising a successful metal complex catalyst to a functionalised support rarely yielded other than an inferior version of the catalyst. Amongst the many discouraging results of the 1970s, there were more than enough results that were sufficiently encouraging to demonstrate that, by careful design, supported metal complex catalysts could be prepared in which both the metal complex and the support combined together to produce an active catalyst which, due to the combination of support and complex, had advantages of activity, selectivity and specificity not found in homogeneous catalysts. Thus a new generation of catalysts was being developed.

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. Mössbauer.- 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.- Analogues of [Rh(PPh3)3Cl].- Other Rhodium(I)-Phosphine Complexes.- Rhodium(I)-Phosphinite Complexes.- Rhodium Carbonyl Complexes.- Organometallic Rhodium Complexes.- Rhodium Carboxylate Complexes.- Rhodium Amide and Imidazole Complexes.- Rhodium Thioether Complexes.- 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.

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Supported Metal Complexes
A New Generation of Catalysts
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