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' = eta(5)-C5H5 (Cp), eta(5)-C5Me5 (Cp*)) with 1/8 equiv of S-8 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 = Ph2PCH2-CH2PPh2). 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)(mu-S)-(mu-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)(mu(2)-CO)(2)(mu(3)-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. (C) 2009 Elsevier B.V. All rights reserved.