Syntheses of new Mo(II) and W(II) mono(hydrosulfido) complexes and their conversion into di- and tetranuclear sulfido-bridged heterobimetallic complexes

Treatment of [Cp′MH(CO)3] (M = Mo, W; Cp′ = η5-C5H5 (Cp), η5-C5Me5 (Cp*)) with 1/8 equiv of S8 in THF, followed by the reaction with dppe under UV irradiation, gave new mono(hydrosulfido) complexes [Cp′M(SH)(CO)(dppe)] (Cp′ = Cp: M = Mo (5), W (6); Cp′ = Cp*: M = Mo (7), W (8); dppe = Ph2PCH2CH2PPh2). When 5 and 6 dissolved in THF were allowed to react with [RhCl(PPh3)3] in the presence of base, heterodinuclear complexes with bridging S and dppe ligands [CpM(CO)(μ-S)(μ-dppe)Rh(PPh3)] (M = Mo (9), W(10)) were obtained. Semi-bridging feature of the CO ligands were also demonstrated. Upon standing in CH2Cl2 solutions, 9 and 10 were converted further to the dimerization products [(CpM)2{Rh(dppe)}2(μ2-CO)2(μ3-S)2] (M = Mo (13), W). Detailed structures of mononuclear 7 and 8, dinuclear 9 and tetranuclear 13 have been determined by the X-ray diffraction.

Reactions of mono(hydrosulfido) complexes [CpM(SH)(CO)(dppe)] (M = Mo, W) with [RhCl(PPh3)3] in the presence of base gave heterodinuclear complexes [CpM(CO)(μ-S)(μ-dppe)Rh(PPh3)], which were converted further to the dimerization products [(CpM)2{Rh(dppe)}2(μ2-CO)2(μ3-S)2].Figure optionsDownload as PowerPoint slide