Heterobimetallic, cubane-like Mo3S4M ' cluster cores containing the noble metals M ' = Ru, Os, Rh, Ir. Unprecedented tri(mu-carbonyl) bridge between ruthenium atoms in [{(eta(5)-C-P ')(3)Mo3S4Ru}(2)(mu-CO)(3)](2+)

Reaction of the methylcyclopentadienyl (Cp ') cluster compound [(eta (5)-CP ')(3)Mo3S4][Pts] (Pts = p-toluenesulfonate) with noble metal alkene comple xes resulted in the formation of four new heterobimetallic cubane-like Mo3S 4M ' cluster cores (M ' Ru, Os, Rh, Ir). Thus, reaction with [(1,5-cod)Ru(C O)(3)] or [(1,3-cod)Os(CO)(3)] (cod = cyclooctadiene) afforded [(eta (5)-CP ')(3)Mo3S4M ' (CO)(2)][Pts] (M ' = Ru: [1][pts]; M ' = Os: [2][pts]). When [1][pts] was kept in CH2Cl2/pentane solution, partial loss of carbonyl lig ands occurred and the carbonyl-bridged dicubane cluster [{(eta (5)-Cp ')(3) Mo3S4Ru}(2)(mu -CO)(3)][pts](2) was isolated. An X-ray crystal structure re vealed the presence of the hitherto unobserved Ru(mu -CO)(3)Ru structural e lement. The formation of cluster compounds containing Mo3S4Rh and Mo3S4Ir c ores was achieved in boiling methanol by reacting [(eta (5)-Cp ')(3)Mo3S4][ Pts] With [M ' Cl(cyclooctene)(2)](2) (M ' = Rh, Ir) in the presence of PPh 3. In this way [(eta (5)-Cp ')(3)Mo3S4][pts] (M ' = Rh, Ir) could be isolat ed. An alternative route to the Mo3S4Rh cluster core was found in the react ion of [(eta (5)-CP ')(3)Mo3S4][Pts] with [RhCl(1,5-cod)](2), which yielded [(eta (5)-Cp ')(3)Mo3S4Rh(cod)][pts](2) ([7][pts](2)). Substitution of the cod ligand in [7][pts](2) by 1,3-bis(diphenylphosphanyl)propane (dppp) gav e [(eta (5)-Cp ')(3)Mo3S4Rh(dppp)][pts](2).