Thermal and photoassisted ring opening of thietane in a triosmium cluster complex

Os{sub 3}(CO){sub 11}[S(CH{sub 2}){sub 3}], 1, is decarbonylated by UV irradiation. Two isomers, Os{sub 3}(CO){sub 10}[{mu}-S(CH{sub 2}){sub 2}CH{sub 2}], 2, and Os{sub 3}(CO){sub 10}[{mu}-S(CH{sub 2})CH=CH{sub 2}]({mu}-H), 3. Thermal reactions of 2 and 3 were heated to produce Os{sub 2}(CO){sub 6}[{mu}-SCH{sub 2}CH{sub 2}CH]({mu}-H) addition of phosphines to 2 yielded Os{sub 3}(CO){sub 10}[{mu}-S(CH{sub 2}){sub 2}](L) (5, L = PPh{sub 3}; 6, L = PMe{sub 2}Ph). The crystal structure of 1, 2, 4, 6, and 7 are reported. 24 refs., 5 figs., 16 tabs.