Reactivity of the heteronuclear cluster Cp*IrOs3(μ-H)2(CO)10 with some group 16 substrates

The mixed metal cluster Cp*IrOs3(μ-H)2(CO)10 (1) reacted readily with a number of group 16 substrates under chemical activation with TMNO. It reacted with C6H5SH to afford the novel cluster Cp*IrOs3(μ-H)3(CO)9(μ-SPh) (2). It also reacted readily with Ph3PSe to afford five new clusters, viz., Cp*IrOs3(μ-H)2(CO)9(μ3-Se) (3) Os3(μ-H)2(CO)7(μ3-Se)(PPh3)2 (4), Cp*IrOs3(μ-H)2(CO)9(PPh3) (5), Cp*IrOs3(μ-H)2(μ3-Se)(CO)8(PPh3) (6) and Cp*IrOs3(μ-H)2(μ3-Se)2(CO)7(PPh3) (7). The reaction pathway for this reaction has been studied carefully and suggests that Ph3PSe functioned primarily as a selenium atom transfer agent to give initially the even more reactive 3. The reaction of 1 with di-p-tolyl ditelluride yielded three new clusters, 8–10, which were non-interconverting stereoisomers with the formulation Cp*IrOs3(μ-H)2(μ-Te-p-C6H4CH3)2(CO)8.