Disulfur-bridged complexes of molybdenum. Crystal structure of the dimolbdenum(IV) complex [{MoCl3(C4H8S)}2(µ-S2)(µ-C4H8S)] and of the MoIVMoV complex [(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 g_max at 1.94.