Reaction of elemental sulphur with bis(pentamethylcyclopentadienyl)vanadium derivatives: disulphido and µ-sulphido complexes. Crystal structures of [V(η-C5Me5)2(S2)] and [V2(η-C5Me5)2Cl2(µ-S)2]

Abstract

Reactions of elemental sulphur with [V(η-C₅Me₅)₂], (1), and [V(η-C₅Me₅)₂Cl], (6), are reported. The compound [V(η-C₅Me₅)₂] reacted with S₈ forming [V(η-C₅Me₅)₂(S₂)], (2)[V–S 2.415(4); S–S 2.028(4)Å; (η-C₅Me₅)–V–(η-C₅Me₅), 141.7(4)°], which is paramagnetic, having one unpaired electron (µ_eff.= 1.89 at 297 K). Desulphurization of (2) with [Fe(salen)][salen =NN′-ethylenebis(salicylideneiminate)] led to [V(η-C₅Me₅)₂] and [{Fe(salen)}₂(µ-S)]. Alkylation of the disulphido ligand with MeSO₃F gave [V(η-C₅Me₅)₂(S₂Me)][SO₃F], (5). Reaction of elemental sulphur with [V(η-C₅Me₅)₂Cl], (6), in tetrahydrofuran, at room temperature gave a mixture of [V(η-C₅Me₅)₂Cl₂], (8), and [V(η-C₅Me₅)₂(S₂)], (2), while reaction in refluxing benzene gave a diamagnetic dimeric vanadium(IV) complex [V₂(η-C₅Me₅)₂Cl₂(µ-S)₂], (9)[V–S 2.16(2) and 2.23(1)Å; V ⋯ V 2.829(3)Å].