The Hydrosulfido-Bridged Diiridium and Dirhodium Complexes [Cp*MCl(μ₂-SH)₂MCp*Cl] (M = Ir, Rh; Cp* = η⁵-C₅Me₅) as Versatile Precursors for Tri- and Tetranuclear Sulfido Clusters

The hydrosulfido-bridged diiridium and dirhodium complexes [Cp*MCl(μ 2 -SH) 2 MCp*Cl] ( 3, M = Ir; 4, M = Rh; Cp* = η 5 -C 5 Me 5 ) were obtained by the reaction of [Cp*MCl(μ 2 -Cl) 2 MCp*Cl] (M = Ir, Rh) with excess H 2 S gas. Treatment of 3 and 4 with NEt 3 gave the cuboidal sulfido clusters [(Cp*M) 4 (μ 3 -S) 4 ] (M = Ir, Rh), while their reaction with [RhCl(cod)] 2 (cod = 1,5-cyclooctadiene) or [Pd(PPh 3 ) 4 ] afforded the cationic triangular sulfido clusters [(Cp*M) 2 Rh(μ 3 -S) 2 (cod)] + (M = Ir, Rh) or [(Cp*Ir) 2 Pd(μ 3 -S) 2 Cl(PPh 3 )] +, respectively.