Wilkinson’s Catalysts

Wilkinson s catalyst [Rh(Ph3P)3Cl]. An important catalyst for homogeneous hydrogenation which also catalyses oxidation by O2 and CO abstraction from organic derivatives. 

Miscellaneous Methods. Exhaustive evaluation of the decarbonylation of ben2oyl duorides, ArCOF, by Wilkinson s catalyst [14694-95-2] Rh[(CgH )2P]3Cl, to give aryl duorides has estabUshed (81) that previous claims (82) caimot be reproduced. 

Dehydrogenative Coupling of Hydride Functional Silanes. The autocouphng of dihydridosilanes was first observed usiag Wilkinson s catalyst (128). A considerable effort has been undertaken to enhance catalyst turnover and iacrease the molecular weight of polysilane products (129) because the materials have commercial potential ia ceramic, photoresist, and conductive polymer technology. 

The Noc group, developed for amino acid protection, is introduced with the acid chloride (Et3N, H2O, dioxane, 2 h, 20°, 61-95% yield). It is cleaved with Pd(Ph3P)4 (THF, A, A -dimethyibarbituric acid, 8 h, 20°, 80% yield). It is not isomerized by Wilkinson s catalyst, thus allowing selective removal of the allyl ester group. 

Wilkinson s catalyst. [RhCKPPhih], This red-violet eompound, which is readily obtained by refluxing ethanolic RhCh.3H20 with an... 

The paramagnetic impurity which invariably accompanies Wilkinson s catalyst has proved difficult to identify. It is probably the air-stable, green, irans- (RhCl(CO)(PPh3)2j- see K. R. Dunbar and S. C Harfner, Innrg. Chem. 31, 36"76-9 (1992),... 

More recently. Baker, Tumas, and co-workers published catalytic hydrogenation reactions in a biphasic reaction mixture consisting of the ionic liquid [BMIM][PFg] and SCCO2 [10]. In the hydrogenation of 1-decene with Wilkinson s catalyst [RhCl(PPh3)3] at 50 °C and 48 bar H2 (total pressure 207 bar), conversion of 98 %... 

Wilkinson s catalyst 117,345,777 Wittig condensation 73 Wittig homologation 503 Wittig methylenation 649 Wittig reaction 17, 68 f., 86 f.,... 

Werner s coordination theory, 1, 6 Whewellite structure, 6, 849 Wickmanite structure, 6, 849 Wilkinson s catalyst, 6, 239 Wilson s disease, 5, 721 copper, 6,648 removal, 6,769 copper complexes, 2,959 copper metabolism, 6,766 radiopharmaceutical agents, 6,968 Wolfram s red salt, 5,427 Wurzite... 

Aldehydes, both aliphatic and aromatic, can be decarbonylated by heating with chlorotris(triphenylphosphine)rhodium or other catalysts such as palladium. The compound RhCl(Ph3P)3 is often called Wilkinson s catalyst.In an older reaction, aliphatic (but not aromatic) aldehydes are decarbonylated by heating with di-tert-peroxide or other peroxides, usually in a solution containing a hydrogen donor, such as a thiol. The reaction has also been initiated with light, and thermally (without an initiator) by heating at 500°C. 

Wilkinson s catalyst has also been reported to decarbonylate aromatic acyl halides at 180°C (ArCOX ArX). This reaction has been carried out with acyl iodides, bromides, and chlorides. Aliphatic acyl halides that lack an a hydrogen also give this reaction, but if an a hydrogen is present, elimination takes place instead (17-16). Aromatic acyl cyanides give aryl cyanides (ArCOCN—> ArCN). Aromatic acyl chlorides and cyanides can also be decarbonylated with palladium catalysts. °... 

The reaction of aldehydes with Wilkinson s catalyst goes through complexes of the form 26 and 27, which have been trapped. The reaction has been shown to give retention of configuration at a chiral and deuterium labeling demonstrates that the reaction is intramolecular RCOD give RD. 

Scheme 4.17 Simplified alkene hydrogenation mechanism using Wilkinson s catalyst...

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