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Homogeneous Catalysis with Compounds of Rhodium and Iridium

  • Fester Einband
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Some years ago, I agreed to contribute a volume to the Academic Press 'Organo metallic Chemistry' series - the metals to be covere... Weiterlesen
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Beschreibung

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.

Inhalt
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 CH and CC 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 CH 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 allylrhodium 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 WaterGas 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 CO 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. AlkeneDiene 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.

Produktinformationen

Titel: Homogeneous Catalysis with Compounds of Rhodium and Iridium
Autor:
EAN: 9789027718808
ISBN: 9027718806
Format: Fester Einband
Herausgeber: Springer Netherlands
Anzahl Seiten: 298
Gewicht: 614g
Größe: H241mm x B160mm x T21mm
Jahr: 1985
Untertitel: Englisch
Auflage: 1985

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