Heterobimetallic,Cubane-like Mo_3S_4M' Cluster Cores Containing the Noble Metals M'=Ru, Os, Rh, Ir. Unprecedented Tri(#mu#-carbonyl) Bridge Between Ruthenium Atoms in [{(#eta#~5-Cp')_3Mo_3S_4Ru}_2(#mu#-CO)_3]~2+

摘要

Reaction of the methylcyclopentadieny1(Cp') cluster compound [(#eta#~5-Cp')_3Mo_3S_4][pts] (pts = #rho#-toluenesulfonate) with noble metal alkene complexes resulted in the formation of four new heterobimetallic cubane-like Mo_3S_4M' 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')_3Mo_3S_4M'(CO)_2][pts] (M' = Ru: [1][pts]; M' = Os:[2][pts]. When [1][pts] was kept in CH_2CL_2/pentane solution, partial loss of carbonyl ligands occurred and the carbonyl-bridged dicubane cluster [{(#eta#~5-Cp')_3Mo_3S_4Ru}_2(#mu#-CO)_3)][pts]_2 was isolated. An X-ray crystal structure revealed the presence of the hitherto unobserved Ru(#mu#-CO)_3Ru structural element. The formation of cluster compounds containing Mo_3S_4Rh and Mo_3S_4Ir cores was achieved in boiling methanol by reacting [(#eta#-Cp')_3Mo_3S_4][pts] with [M'Cl(cyclooctene)_2]_2(M' = Rh, Ir) in the presence of PPh_3. In this way [(#eta#-Cp')_3Mo_3S_4M'Cl(PPh_3)][pts] (M' = Rh, Ir) could be isolated. An alternative route to the Mo_3S_4Rh cluster core was found in the reaction of [(#eta#-Cp')_3Mo_3S_4][pts] with [RhCl(1,5-cod)]_2, which yielded[(#eta#-Cp')_3Mo_3S_4Rh(cod)][pts]_2([7][pts]_2). Substitution of the cod ligand in [7][pts]_2 by 1,3-bis(diphenylphosphanyl)propane (dppp) gave [(#eta#-Cp')_3Mo_3S_4Rh(dppp)][pts]_2.