Heterobimetallic, cubane-like Mo(3)S(4)M' cluster cores containing the noble metals M' = Ru, Os, Rh, Ir. Unprecedented tri(mu-carbonyl) bridge between ruthenium atoms in [(eta(5)-Cp')(3)Mo(3)S(4)Ru)2(mu-CO)3]2+

Reaction of the methylcyclopentadienyl (Cp') cluster compound (eta(5)-Cp')(3)Mo(3)S(4)]pts] (pts = p-toluenesulfonate) with noble metal alkene complexes resulted in the formation of four new heterobimetallic cubane-like Mo(3)S(4)M' cluster cores (M' = Ru, Os, Rh, Ir). Thus, reaction with (1,5-cod)Ru(CO)(3)] or (1,3-cod)Os(CO)(3)] (cod = cyclooctadiene) afforded (eta(5)-Cp')(3)Mo(3)S(4)M'(CO)(2)]pts] (M' = Ru: 1]pts]; M' = Os: 2]pts]). When 1]pts] was kept in CH(2)Cl(2)/pentane solution, partial loss of carbonyl ligands occurred and the carbonyl-bridged dicubane cluster ((eta(5)-Cp')(3)Mo(3)S(4)Ru)(2)(mu-CO)(3)]pts](2) was isolated. An X-ray crystal structure revealed the presence of the hitherto unobserved Ru(mu-CO)(3)Ru structural element. The formation of cluster compounds containing Mo(3)S(4)Rh and Mo(3)S(4)Ir cores was achieved in boiling methanol by reacting (eta(5)-Cp')(3)Mo(3)S(4)]pts] with M'Cl(cyclooctene)(2)](2) (M' = Rh, Ir) in the presence of PPh(3). In this way (eta(5)-Cp')(3)Mo(3)S(4)M'Cl(PPh(3))]pts] (M' = Rh, Ir) could be isolated. An alternative route to the Mo(3)S(4)Rh cluster core was found in the reaction of (eta(5)-Cp')(3)Mo(3)S(4)]pts] with RhCl(1,5-cod)](2), which yielded (eta(5)-Cp')(3)Mo(3)S(4)Rh(cod)]pts](2) (7]pts](2)). Substitution of the cod ligand in 7]pts](2) by 1,3-bis(diphenylphosphanyl)propane (dppp) gave (eta(5)-Cp')(3)Mo(3)S(4)Rh(dppp)]pts](2).