Reactions of hydrosulfido- and hydroselenido-bridged dinuclear Ir, Rh, and Ru complexes with SbCl3 and BiCl3 affording mixed-metal sulfido and selenido clusters containing both noble metals and Group 15 metals

A new versatile method to synthesize a series of noble metal-Group 15 metal chalcogenido clusters has been found. Thus, treatment of the hydrosulfido- or hydroselenido-bridged dinuclear complexes [Cp*MCl(μ-EH)2MCp*Cl] (M=Ir, Rh; E=S, Se; Cp*=η5-C5Me5), [Cp°RuCl(μ-SH)2RuCp°Cl] (Cp°=η5-C5EtMe4), and [Ru(L)Cl(μ-SH)2Ru(L)Cl] (L=η6-C6Me5H) with M′Cl3 (M′=Sb, Bi) in THF at room temperature afforded smoothly the clusters [Cp*MCl(μ-EM′Cl2)2MCp*Cl], [Cp°RuCl(μ-SM′Cl2)2RuCp°Cl], and [Ru(L)Cl(μ-SM′Cl2)2Ru(L)Cl] through dehydrochlorination. The X-ray analyses of eleven new clusters clarified the details of their structures consisting of the cubane-type M2M′2E2Cl2 cores resulting from the presence of weak MCl⋯M′ bonding interactions in addition to the normal M–E, M–Cl, and M′–E bonds.