Abstract

Isolation of the doubly unsaturated mono(sulfonylimido)-bridged diiridium(II) complex [(Cp*Ir)2(μ2-NMs)] (5; Cp* = η5-C5Me5, Ms = SO2Me), which would be generated by 2-fold dehydrochlorination of the sulfonylamido-bridged diiridium(III) complex [(Cp*IrCl)2(μ2-H)(μ2-NHMs)] (2), was attempted. Treatment of 2 with 2 equiv of a base in the presence of trimethylphosphine afforded the mono(phosphine) adduct [(Cp*Ir)2(μ2-NMs)(PMe3)] (6), while dehydrochlorination of 2 with dimethylzinc and silver acetate led to the formation of the mixed-metal clusters [(ZnCl2)(Cp*Ir)2(μ2-NMs)] (7) and [(AgCl)2(μ2-Cl)2Ag2{(Cp*Ir)2(μ2-NMs)}2] (8), respectively. The detailed structures of 6–8, containing the imido-bridged diiridium(II) core of 5, have been determined by X-ray analysis.

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