Abstract

The reaction of Cp‘ReCl4 (Cp‘ = EtMe4C5) with 2−3 equiv of bis(trimethylsilyl)sulfide in chloroform in the presence of an oxidant results in the formation of Cp‘Re(η2-S3)Cl2, 2. Complex 2 has been characterized by spectroscopic methods, and its structure has been confirmed by an X-ray diffraction study. Complex 2 reacts with hydrogen under mild conditions to form H2S, HCl, and a rhenium product tentatively identified as (Cp‘Re)2S4, 3. Complex 3 reacted with benzyl bromide to form [(Cp‘Re)2(μ-S2)(μ-SCH2Ph)2]Br2, 4, which has been completely characterized by spectroscopic studies and an X-ray crystal structure. The structures and reactions of the Cp‘Re derivatives with sulfur ligands are compared to those of the related tetrasulfur-bridged CpMo derivatives.

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