Homogeneous Catalysis with Compounds of Rhodium and Iridium

Some General Comments on Transition Metal Catalysts.- 1.1. Catalysts and Catalyst Recovery.- 1.2. Supported Catalysts.- Chemisorption of CO on supported rhodium.- 1.3. Organic Feedstocks.- 1.4. Organic Reactions Catalysed by Rhodium and Iridium Compounds.- The Activation of C-H and C-C Bonds: Dehydrogenation, H/D Exchange and Isomerization Reactions.- 2.1. The Activation of C - H Bonds in Saturated Hydrocarbons.- 2.2. Dehydrogenation.- 2.3. H/D Exchange.- 2.4. Unsaturated Alcohol to Aldehyde Conversions.- 2.5. Double-bond Migration.- Catalyst sources.- Relative activities and rates.- Mechanisms.- 2.6. Geometric cis ? trans Isomerization.- 2.7. Intermodular Disproportionation Reactions.- Alkenes.- Aldehydes, ethers and esters.- 2.8. Valence Isomerization; Ring-opening Reactions.- The Formation of C-H Bonds: Hydrogenation and Related Reactions.- 3.1. RhCl(PPh3)3 and HRh(PPh3) a.- The catalyst systems.- Reaction pathways.- Range of alkenes and relative rates.- Stereochemistry and regioselectivity of addition.- Catalysts related to RhCl(PPh3)3.- 3.2. M(CO)XL2.- 3.3. HM(CO)(PPh3)3.- 3.4. Other Catalysts with Carbonyl and Related ?-Acid Ligands.- 3.5. Catalysts Derived from Alkene and Diene Complexes of RhI and IrI.- Formation of catalysts from [M(alkene)2 Cl] 2; hydrogenation of alkenes and related substrates.- Formation of catalysts from [M(diene)Cl] 2.- Catalysts derived from allyl-rhodium complexes.- 3.6. Complexes of MIII as the Catalyst Source.- {RhCl3py3 + NaBH4}.- (?-C5Me5)MIII complexes.- Hydrido-IrIII complexes; Ha IrXbLc.- Miscellaneous RhIII complexes.- 3.7. Catalysts Derived from RhII, Rh24+.- 3.8. Reductions via H-transfer from Alcoholic Solvents.- 3.9. Supported Hydrogenation Catalysts.- Polymeric supports.- High surface area oxide supports.- Catalysts attached to silicone polymers.- 3.10. Asymmetric Homogeneous Hydrogenation with Chiral Rhodium Complexes as Catalysts.- Requirements for asymmetric synthesis; an overview.- Catalyst types.- Polymer supports with chiral ligands.- Factors affecting enantioselectivity.- Key intermediates.- A commercial application; the synthesis of L-dopa.- The asymmetric reduction of ketones.- 3.11. Hydrosilation Reactions.- Homogeneous catalysts.- Polymer-supported catalysts.- Asymmetric hy drosilation.- Hydrogermylation.- Addition of amines to carbonyl compounds.- Carbonylation and Hydroformylation Reactions.- 4.1. The Water-Gas Shift Reaction.- 4.2. The Hydrogenation of CO; Synthesis Gas Chemistry.- Reaction products.- Catalysts.- Mechanism.- 4.3. The Catalytic Reduction of NO by CO.- 4.4. Carbonylation Reactions.- Conversion of alcohols to carboxylic acids and esters.- Reactions of ethers, esters and related compounds.- Carbonylation of organic halides.- Carbonylation of nitroso and azido compounds; the formation of isocyanates.- Carbonylation of organic amines.- Carbonylation of cyclic, polycyclic and unsaturated hydrocarbons.- Carbonylation of organomercury compounds; the formation of ketones.- 4.5. Hydroformylation; the Formation of Aldehydes from Alkenes.- Hydroformylation catalysts.- Some special applications of the hydroformylation reaction.- Oxidation Reactions.- 5.1. Direct Reaction with O2.- 5.2. Other Means of Forming C-O Bonds.- Functional Group Removal.- 6.1. Decarbonylation.- 6.2. Desulfonylation.- 6.3. Deoxygenation, including the Decomposition of Hydroperoxides.- Oligomerization, Polymerization and Related Condensation Reactions.- 7.1. Alkene Dimerization and Polymerization.- 7.2. Diene Oligomerization and Polymerization.- 7.3. Alkene-Diene Co-oligomerization.- 7.4. Oligomerization and Polymerization of Cyclic Alkenes and Polyenes, including Ring-opening Reactions.- 7.5. The Oligomerization, Polymerization and Addition Reactions of Alkynes.- 7.6. The Formation of Functionalized Oligomers and Polymers.- 7.7. Other Reactions Leading to the Formation of New C -X Bonds.- Alkylation (and arylation) reactions.- Reactions involving carbene precursors.- Addition, cyclization and related reactions involving aldehydes.- Alkylation, cyclization and related reactions involving alcohols.- Other cyclization reactions.- Coupling reactions.- Appendix. Tabulation of Catalysts and their Applications.- References.