Cyclopentadienyl (Cp), hydrotris(pyrazolyl)borato (Tp), and bipyridine ruthenium complexes were found to be active catalysts for the b-alkylation of secondary alcohols with primary alcohols. Mechanistic aspects of the Cp and Tp complexes-catalyzed reactions were investigated; the crucial hydrido complexes were identified. Carbonyl complexes resulting from aldehyde decarbonylation were formed in some cases, and surprisingly, they were also found to be active for the catalytic processes.
An X‐ray crystallographic study showed that it is more appropriate to describe the complexes TpRu(PPh3)“H2SiR3” as TpRu(PPh3)(η3‐HSiR3H), a static structure containing H···Si···H bonding rather than a highly fluxional pair ofσ‐silane hydride species TpRu(PPh3)(Ha)(η2‐HbSiR3) [rlhar2] TpRu(PPh3)(Hb)(η2‐HaSiR3). One of the complexes was used for the catalytic hydrolytic oxidation of organosilanes to silanols. A mechanism, which does not involve the usual oxidative addition of silane to the metal center to form the silyl hydride species, is proposed, which is supported by theoretical calculations.
Alcohols Q 0230Ruthenium-Catalyzed β-Alkylation of Secondary Alcohols with Primary Alcohols. -Bipyridine, cyclopentadienyl, and hydrotris(pyrazolyl)borato ruthenium complexes are found to be active catalysts with [Ru(H2O)2(6,6'-Cl2-bipy)2](OTf)2 being the most active one. The mechanism of the alkylation is discussed and it is demonstrated, that carbonyl complexes resulting from aldehyde decarboxylation are also active for the alkylation reactions. -(CHEUNG, H. W.; LEE, T. Y.; LUI, H. Y.; YEUNG, C. H.; LAU*, C. P.; Adv.
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