Oxygen atom transfer reactions from dioxygen to phosphines via a bridging sulfur dioxide in a trinuclear cluster complex of rhenium, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)].

A trinuclear rhenium sulfide cluster complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(3)Cl(6)(PMe(2)Ph)(3)], synthesized from Re(3)S(7)Cl(7), dimethylphenylphosphine, and [(Ph(3)P)(2)N]Cl is readily converted to a bridging SO(2) complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)], by reaction with O(2). The oxygen atoms on the SO(2) ligand react with phosphines or phosphites to form phosphine oxides or phosphates, and the original cluster complex is recovered. The reaction course has been monitored by (31)P NMR as well as by UV-vis spectroscopy. The catalytic oxygenation of PMePh(2) in the presence of the SO(2) complex shows that turnovers are 8 per hour at 23 degrees C in CDCl(3). The X-ray structures of the cluster complexes are described.