Syntheses of a CpRe=S Derivative and More Complex Products

The reaction of CpʹReC2S3 (Cp" = Me4EtC5) with slightly less than 2 equiv of a phosphine reagent results in the formation of [CpʹRe(CI)2(-S)]2, 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type CpʹReS(CI)2(Nuc). The reaction of CpʹReCl2(SC2H4S) with (Me3Si)2S resulted in the formation of three new products: CpʹReS(SC2H4S), 4; CpʹRe(S3)(SC2H4S), 5; and a tetranuclear derivative, 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues.