Dinuclear, trinuclear and mixed-metal hexanuclear aggregates of vanadium: crystal structures and properties of [NEt4]3[V2Cl9], [PPh4]2[V3OCl4(O2CC6H4SH)5] and [NEt4]4[V2Li4O2Cl4(O2CC6H4S)4]†

Abstract

The reaction between [VCl₃(thf)₃] and Cl^– provided a high-yield route to [NEt₄]₃[V₂Cl₉] 1, which contains a [V₂(µ-Cl)₃Cl₆]^3– face-sharing bioctahedron. The reaction of [VCl₃(thf)₃] with sodium 2-sulfanylbenzoate (mba^2–) in the presence of water and PPh₄Cl gave [PPh₄]₂[V₃OCl₄(Hmba)₅] 2, whose anion contains a triangular [V₃(µ₃-O)]⁷⁺ core. The reaction of [NEt₄]₂[VOCl₄] with H₂mba and Li₂S gave [NEt₄]₄[V₂Li₄O₂Cl₄(mba)₄] 3, whose anion contains two [VO(mba)] fragments bridged by a [Li₄Cl₄] unit. Compounds 1 and 2 are weakly antiferromagnetically coupled with J = –13.4(4) and –3.2(1.6) cm^–1, respectively (Ĥ = –2JS_iS_j convention).