Thiochlorowolframates with tungsten(V) and (VI)

Diamagnetic (NEt4)2[WSCl4]2, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl5 with NEt4SH as well as by the reduction of WSCl4 with NEt4I in dichloromethane. If the reduction is performed with PPh4I, PPh4[WSCl4] with monomer anions is formed. Reaction of WCl6 with H2S in dichloromethane yields brown, insoluble WS2Cl2 which has terminal W=S groups and bridging W-S-W groups according to its IR spectrum. WS2Cl2 and PPh4Cl react to afford PPh4[WS2Cl2] · 2 CH2Cl2 and (PPh4)2[WS2Cl4] · 2 CH2Cl2. IR spectra are reported. The crystal structures of PPh4[WSCl4] and (PPh4)2[WS2Cl4] · 2 CH2Cl2 were determined by X-ray diffraction. PPh4[WSCl4]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl4]- ion has the structure of a square pyramid with a rather short W=S bond of 206 pm length. (PPh4)2[WS2Cl4] · 2 CH2Cl2: triclinic, space group P-1, a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.800; R = 0.076 for 1804 reflexions. The [WS2Cl4]2- has cis configuration; as it is situated on an inversion center it shows positional disorder. (author)