Visible-light irradiation at the longest-wavelength absorption band (λmax = 475 nm) of the A-frame dinuclear complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane] caused catalytic dehydrogenation of cyclooctane [initial turnover frequency = 32.8 h-1, total turnover number = 27.3 (per complex)]. The absorption band effective for photocatalysis was assigned to a metal-to-ligand charge transfer (m.l.c.t.) by extended Hückel molecular orbital (EHMO) calculations. The m.l.c.t. transition energy of [Rh2(μ-S)(CO)2(dppm)2] was lower than that of the photocatalytically active mononuclear complex [RhCl(CO)(PPh3)2] (λmax = 364 nm), the origin of which was investigated in detail in terms of the Rh-Rh and Rh-S interactions.
|Number of pages||5|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Publication status||Published - Dec 1 1993|
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