Heterobimetallic, Cubane-like Mo<sub>3</sub>S<sub>4</sub>M‘ Cluster Cores Containing the Noble Metals M‘ = Ru, Os, Rh, Ir. Unprecedented Tri(μ-carbonyl) Bridge Between Ruthenium Atoms in [{(η<sup>5</sup>-Cp‘)<sub>3</sub>Mo<sub>3</sub>S<sub>4</sub>Ru}<sub>2</sub>(μ-CO)<sub>3</sub>]<sup>2+</sup>
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Reaction of the methylcyclopentadienyl (Cp‘) cluster compound [(η5-Cp‘)3Mo3S4][pts] (pts = p-toluenesulfonate) with noble metal alkene complexes resulted in the formation of four new heterobimetallic cubane-like Mo3S4M‘ 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 [(η5-Cp‘)3Mo3S4M‘(CO)2][pts] (M‘ = Ru: [1][pts]; M‘ = Os: [2][pts]). When [1][pts] was kept in CH2Cl2/pentane solution, partial loss of carbonyl ligands occurred and the carbonyl-bridged dicubane cluster [{(η5-Cp‘)3Mo3S4Ru}2(μ-CO)3][pts]2 was isolated. An X-ray crystal structure revealed the presence of the hitherto unobserved Ru(μ-CO)3Ru structural element. The formation of cluster compounds containing Mo3S4Rh and Mo3S4Ir cores was achieved in boiling methanol by reacting [(η5-Cp‘)3Mo3S4][pts] with [M‘Cl(cyclooctene)2]2 (M‘ = Rh, Ir) in the presence of PPh3. In this way [(η5-Cp‘)3Mo3S4M‘Cl(PPh3)][pts] (M‘ = Rh, Ir) could be isolated. An alternative route to the Mo3S4Rh cluster core was found in the reaction of [(η5-Cp‘)3Mo3S4][pts] with [RhCl(1,5-cod)]2, which yielded [(η5-Cp‘)3Mo3S4Rh(cod)][pts]2 ([7][pts]2). Substitution of the cod ligand in [7][pts]2 by 1,3-bis(diphenylphosphanyl)propane (dppp) gave [(η5-Cp‘)3Mo3S4Rh(dppp)][pts]2.
