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

Abstract

The hydrosulfido-bridged diiridium and dirhodium complexes [Cp*MCl(μ2-SH)2MCp*Cl] (3, M = Ir; 4, M = Rh; Cp* = η5-C5Me5) were obtained by the reaction of [Cp*MCl(μ2-Cl)2MCp*Cl] (M = Ir, Rh) with excess H2S gas. Treatment of 3 and 4 with NEt3 gave the cuboidal sulfido clusters [(Cp*M)4(μ3-S)4] (M = Ir, Rh), while their reaction with [RhCl(cod)]2 (cod = 1,5-cyclooctadiene) or [Pd(PPh3)4] afforded the cationic triangular sulfido clusters [(Cp*M)2Rh(μ3-S)2(cod)]+ (M = Ir, Rh) or [(Cp*Ir)2Pd(μ3-S)2Cl(PPh3)]+, respectively.