Thiol exchange for MO3+(M = Mo or W) centres; synthesis and structure of [PPh4][MO(SCH2CH2S)2]

Abstract
Stoicheiometric thiol exchange between [MO(SPh)4](M = Mo or W) and HSCH2CH2SH provides a convenient synthesis for the [MO(SCH2CH2S)2] complexes: the structures of the [PPh4]+ salts of these anions have been determined to provide a clear structural comparison between these homologues [the two anions have very similar dimensions Mo–O 1.678(5), W–O 1.641(10), Mo–S 2.372(3), W–S 2.363(6)Å]; on the basis of e.s.r. spectroscopic studies, it is concluded that [MoO(SCH2CH2S)2] is formed when [MoO4]2– reacts with HSCH2CH2SH and when this dithiol reacts with the oxidised molybdenum centre of xanthine oxidase.

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