The Reactivity of Tungsten Halides with Organic Sulfides: S-Dealkylation and Reductive Elimination Reactions

Abstract

Tungsten hexa- or pentachloride reacts with alkyl sulfides to give (R3S)2[WCl6]. The reactions involve S-dealkylation followed by reductive elimination of R2S2. Alkylation of R2S by RCl probably occurs at the tungsten site through the intermediacy of WCl4(R2S)2. The latter compounds have been shown to be unstable with respect to displacement of the sulfide ligands by halide ions or neutral donors and therefore form excellent intermediates for W(IV) synthetic chemistry.