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The attachment of σ-2-thienyl and σ-2-benzothienyl ligands (but not σ-3-thiophenyl ligands) to W26+ containing centres leads to the stepwise opening of the five-membered ring to generate, in the presence of tert-butyl alcohol, a novel thiolato-µ-alkylidyne metallocylcle in W2(OBut)5(µ-SC4H3)(η1-2-SC4H3), which has been structurally characterized; the intermediate W2(OBut)4(µ-SC4H3)(η1-2-SC4H3), which contains a bridging thiolato–vinylidene metallocycle has been characterized by NMR spectroscopy.
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Chisholm et al. (1994) studied this question.
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