Syntheses of a Cp‘ReS Derivative and More Complex Products

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(μ-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)2S resulted in the formation of three new products:  Cp‘ReS(SC2H4S), 4; Cp‘Re(S3)(SC2H4S), 5; and
a tetranuclear derivative, [(Cp‘Re)2(μ-S)(μ,η2-SC2H4S)(μ,η1-SC2H4S]2Cl2, 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.