Two W/Cu/S clusters: tetraethylammonium bromidodi-μ2-sulfido-sulfido[tris(3,5-dimethylpyrazol-1-yl)borato]copper(I)tungsten(VI) and tetraethylammonium dibromido-μ3-sulfido-di-μ2-sulfido-[tris(3,5-dimethylpyrazol-1-yl)borato]dicopper(I)tungsten(VI)

Abstract

The reaction of (Et(4)N)[Tp*WS(3)] [Tp* = hydrogen tris(3,5-dimethylpyrazol-1-yl)borate] with one or two equivalents of CuBr afforded the [1 + 1] and [1 + 2] addition products (Et(4)N)[Tp*WS(μ-S)(2)(CuBr)] {or (C(8)H(20)N)[CuWBr(C(15)H(22)BN(6))S(3)], (I)} and (Et(4)N)[Tp*W(μ(3)-S)(μ-S)(2)(CuBr)(2)] {or (C(8)H(20)N)[Cu(2)WBr(2)(C(15)H(22)BN(6))S(3)], (II)}. The anion of (I) contains a [W(μ-S)(2)Cu] core formed by the addition of one CuBr unit to the [Tp*WS(3)] species. The anion of (II) has a butterfly-shaped [W(μ(3)-S)(μ-S)(2)Cu(2)] core formed by the addition of two CuBr units to the [Tp*WS(3)] species. The [Tp*WS(3)] sections of each complex exhibit approximate C(3v) point symmetry and have closely comparable geometry. In (II), both the anion and cation lie on a crystallographic mirror plane. The structure of (I) is noncentrosymmetric and polar.