The reaction of Cp'ReCl2S3 (CP' = Me4EtC5) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-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 Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl2(SC2H4S) with (Me3Si)(2)S resulted in the formation of three new products: Cp'ReS(SC2H4S), 4; Cp'Re(S-3)(SC2H4S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S) (mu,eta(2)-SC2H4S)(mu,eta(1)-SC2H4S](2)Cl-2, 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.