Synthesis and X-ray structures of heptanuclear and decanuclear mixed-metal sulfido clusters containing noble metals and Group 15 metals

Reactions of incomplete cubane-type clusters [(Cp°RuCl)2(μ-SH)(μ-SM′Cl2)] (M′ = Sb (2a), Bi; Cp° = η5-C5Me4Et) with 0.5 equiv of [PdCl2(cod)] (cod = 1,5-cyclooctadiene) afforded the corner-shared double cubane-type clusters [{(Cp°Ru)(Cp°RuCl)(μ-SM′Cl2)}2(μ3-S)2(μ-Cl)2Pd] (3a: M′ = Sb, 3b: M′ = Bi) in moderate yields, whereas treatment of 2a with 0.75 equiv of [PdCl2(cod)] gave the corner-shared triple cubane-type cluster [{(Cp°Ru)(Cp°RuCl)(μ-SSbCl2)(μ3-S)2(μ-Cl)2Pd}2(Cp°Ru)2] (4). Single-crystal X-ray analyses have disclosed the detailed structures of novel heptanuclear and decanuclear mixed-metal cores for 3a and 4, respectively.