Thiotungstates containing the syn-[W2(O/S)2(μ-S)2] (E = O, S) and cuboidal [W2Cu2(μ3-S)4] cores

Reaction of [WVIS4]2− with ethane-1,2-dithiol edtH2 in the presence of the sulfide scavenger Cd2+ yielded the dinuclear tungstate syn -[{(edt)WV(O/S)}2(μ-S)2]2− (1), with the terminal S/O disordered over the two tungsten sites in the ratio 0.8:02. In the presence of thiocyanate, phosphine and CuI, the anionic cuboidal clusters of composition [{(SCN)3WV}2{CuI(PPh3)}2(μ3-S)4]2− (2) and View the MathML source[{(SCN)3WV}2{Cu2I(μ-diphos)}(μ3-S)4]2- (3, diphos = 1,2-bis(o-diphenylphosphinophenyl)ethane), and possibly via an intermediate [{(SCN)3WVS}2(μ-S)2]4−. The crystal and molecular structures of [Et4N]21, [Et4N]22 · H2O and [Et4N]23 · H2O have been determined.