Mono(sulfido)-bridged mixed-valence nitrosyl complex: protonation and oxidative addition of iodine across the Ir(II)–Ir(0) bond

Treatment of [Cp*IrH(SH)(PMe3)] (Cp* = eta5-C5Me5) with [IrCl2(NO)(PPh3)2] in the presence of triethylamine yielded the sulfido-bridged IrIIIr0 complex [Cp*Ir(PMe3)(mu-S)Ir(NO)(PPh3)], which further reacted with I2 and triflic acid to give the diiodo complex [Cp*Ir(PMe3)(mu-I)(mu-S)IrI(NO) (PPh3)] and the hydrido complex [Cp*Ir(PMe3)(mu-H)(mu-S)Ir(NO)(PPh3)][OSO2CF3], respectively.