Trapping of a Doubly Unsaturated Dinuclear Iridium(II) Sulfonylimido Complex with Phosphine and Lewis Acidic Group 11 and 12 Metals

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.