Homogeneous Catalysis With Compounds of Rhodium and Iridium: 8 - Rilegato

Dickson, Ronald S.

Rilegato

ISBN 10: 9027718806 ISBN 13: 9789027718808

Casa editrice: D Reidel Pub Co, 1985

Riassunto

Some years ago, I agreed to contribute a volume to the Academic Press 'Organo­ metallic Chemistry' series - the metals to be covered were rhodium and iridium. Initially, my plan was to discuss both the fundamental organometallic chemistry and applications in organic synthesis. When the first draft of the manuscript was complete, it was apparent that I had exceeded my allowance of pages by a huge amount. It was then that I decided that the catalysis section warranted separate treatment. I am grateful to Reidel for agreeing to publish this volume on Homogeneous Catalysis with Compounds of Rhodium and Iridium as part of their 'Catalysis by Metal Complexes' series. The material I had for the original Academic Press project covered the litera­ ture to the end of 1978. I decided to update this to the end of 1982 with a few key references from 1983. It is some measure of the rate of progress in this field that the number of references almost doubled during this revision.

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Recensione

`...provides a very readable and useful review of the present state of knowledge on catalysis involving rhodium and iridium species. Literature up to 1982 is comprehensively covered and very clear mechanistic schemes are provided, while in addition a helpful tabulation of homogeneous catalysts and their applications is presented as an Appendix.' Platinum Metals Review (1986)

Contenuti

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.

Dettagli dell'edizione

• Editore: D Reidel Pub Co
• Data di pubblicazione: 1985
• Lingua: Inglese
• ISBN 10: 9027718806
• ISBN 13: 9789027718808
• Rilegatura: Copertina rigida
• Numero di pagine: 298
• Contatto del produttore: ProductSafety@springernature.com; ProductSafety@springernature.com; ; Poststr. 9; Darmstadt; 64293; Germania