Disulfur-bridged complexes of molybdenum. Crystal structure of the dimolbdenum(IV) complex [{MoCl3(C4H8S)}2(µ-S2)(µ-C4H8S)] and of the MoIVMoVcomplex [(Me2S)2Cl2Mo({µ-S2)(µ-S)MoCl3(SMe2)

Abstract

Treatment of [Mo(CO)6] with S2Cl2 gave a very dark green material of empirical formula Mo2S2Cl6·CH2Cl21 which, on reaction with L, gave green [{MoCl3(L)}2(µ-S2)(µ-L)](L = C4H8S 2a, PhCH2SMe 2b or C4H8O 2c), and with SMe2 gave the novel, brown, unsymmetrical, mixed-oxidation-state complex [(Me2S)2Cl2Mo(µ-S2)(µ-S)MoCl3(SMe2)]3. The structures of 2a and 3 have been established by X-ray crystallography. Compounds 2a–2c are diamagnetic and NMR data have been obtained, whereas 3 is paramagnetic and shows, in a CH2Cl2 glass at 40 K, a broad, roughly axial EPR resonance with gmax at 1.94.