Reactions of molybdenum oxo-thioclusters with [Re(CO)5Cl]

Reduction of [Mo2O2(μ-S)2(H2O)6]2+ with [Re(CO)5Cl] in 2 М HCl at 160 °C produces condensation of binuclear clusters with the formation of the{Mo3(μ3-S)(μ-O)3}4+ species, which was isolated and structurally characterized as {[Mo3(μ3-S)(μ2-O)3(H2O)6Cl3]2CB[6]}Cl2·10.88H2O (2) (CB[6] = C36H36N24O12) and [Mo3(μ3-S)(μ2-O)3(acac)3(py)3]PF6·2C6H5CH3 (3). Reaction of [Mo3(μ3-S)(μ2-S)(μ2-O)2(H2O)9]4+ with [Re(CO)5Cl] produces cuboidal cluster [Mo4(μ3-S)4(H2O)12]5+.

Graphical abstractReduction of [Mo2O2(μ-S)2(H2O)6]2+ with [Re(CO)5Cl] produces {Mo3(μ3-S)(μ-O)3}4+, which was isolated and structurally characterized as adduct with CB[6] (CB[6] = C36H36N24O12) and [Mo3(μ3-S)(μ2-O)3(acac)3(py)3]PF6·2C6H5CH3. Reaction of [Mo3(μ3-S)(μ2-S)(μ2-O)2(H2O)9]4+ with [Re(CO)5Cl] produces [Mo4(μ3-S)4(H2O)12]5+.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Reduction of [Mo2O2S2(H2O)6]2+ with [Re(CO)5Cl] produces {Mo3(μ3-S)(μ-O)3}4+ (M3). ► X-ray analysis of M3 adduct with C36H36N24O12 and [M3(acac)3(py)3]+. ► Calculations: Multicentered banana-like Mo–Mo bonding in the M3. ► Reaction of [Mo3S2O2(H2O)9]4+ with [Re(CO)5Cl] produces [Mo4S4(H2O)12]5+.