Reactions of the pentamethylcyclopentadienyl trisulfido tungsten with M′Cl2 (M′ = Zn, Cd, Hg): Isolation and structural characterization of [PPh4][(η5-C5Me5)WS3(ZnCl2)] and [{(η5-C5Me5)WS3}2Hg]

Reactions of [PPh4][(η5-C5Me5)WS3] with equimolar M′Cl2 (M′ = Zn, Cd) in MeCN or 0.5 equiv. of HgCl2 in DMF afforded two binuclear clusters [PPh4][(η5-C5Me5)WS3(M′Cl2)] (1: M′ = Zn; 2: M′ = Cd) and one trinuclear cluster [{(η5-C5Me5)WS3}2Hg] (3). Compounds 1–3 were characterized by elemental analysis, IR, UV–Vis, 1H NMR and X-ray crystallography. Compound 1 may be viewed as a 1:1 composite of [PPh4][(η5-C5Me5)WS3] and ZnCl2, in which one [(η5-C5Me5)WS3]− anion binds a ZnCl2 moiety via two μ-S atoms. In the structure of 3, two [(η5-C5Me5)WS3]− anions coordinate the central Hg atom via two μ-S atoms, forming an unique bent linear structure. In addition, internal redox reactions of [PPh4][(η5-C5Me5)WS3] under the presence of M′Cl2 (M′ = Zn, Cd, Hg) in high concentrations were discussed.