PHOTOINDUCED C-C BOND FORMATION FROM ALKYL-HALIDES CATALYZED BY LUMINESCENT DINUCLEAR GOLD(I) AND COPPER(I) COMPLEXES

The photoluminescent properties of [Au2(mu-dppm)2]2+ [dppm = bis(diphenylphosphino)methane], [Au2(mu-dmpm)3]2+ [dmpm = bis(dimethylphosphino)methane] and [Cu2(mu-dPPM)2(MeCN)4]2+ have been investigated. Irradiation of a degassed acetonitrile solution of benzyl chloride or 1-bromopentane in the presence of a sacrificial electron donor such as triethylamine and a catalytic amount of [Au2(mu-dppm)2]2+ led to the formation of bibenzyl or n-decane. Similar photoreactions with much lower yields of the C-C bond coupling products have also been observed with [Au2(mu-dmpm)3]2+ and [Cu2(mu-dppm)2(MeCN)4]2+ as catalysts. The mechanism of the photoreaction between alkyl halides and [Au2(mu-dppm)2]2+ has been investigated by steady-state photolysis, Stern-Volmer quenching and flash-photolysis studies.