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]

The reaction between [VCl3(thf)(3)] and Cl- provided a high-yield route to [NEt4](3)[V2Cl9] 1, which contains a [V-2(eta-Cl)(3)Cl-6](3-) face-sharing bioctahedron. The reaction of [VCl3(thf)3] with sodium 2-sulfanylbenzoate (mba(2-)) in he presence of water and PPh4Cl gave [PPh4](2)[V3OCl4(Hmba)(5)] 2, whose anion contains a triangular [V-3(mu(3)-O)](7+) core. The reaction of [NEt4](2)[VOCl4] with H(2)mba 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 ((H) over cap = -2JS(i)S(j) convention).