Reactions of the pentamethylcyclopentadienyl trisulfido tungsten with M′Cl 2 (M′ = Zn, Cd, Hg): Isolation and structural characterization of [PPh 4][(η 5-C 5Me 5)WS 3(ZnCl 2)] and [{(η 5-C 5Me 5)WS 3} 2Hg

Abstract

Reactions of [PPh 4][(η 5-C 5Me 5)WS 3] with equimolar M′Cl 2 (M′ = Zn, Cd) in MeCN or 0.5 equiv. of HgCl 2 in DMF afforded two binuclear clusters [PPh 4][(η 5-C 5Me 5)WS 3(M′Cl 2)] ( 1: M′ = Zn; 2: M′ = Cd) and one trinuclear cluster [{(η 5-C 5Me 5)WS 3} 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 [PPh 4][(η 5-C 5Me 5)WS 3] and ZnCl 2, in which one [(η 5-C 5Me 5)WS 3] − anion binds a ZnCl 2 moiety via two μ-S atoms. In the structure of 3, two [(η 5-C 5Me 5)WS 3] − anions coordinate the central Hg atom via two μ-S atoms, forming an unique bent linear structure. In addition, internal redox reactions of [PPh 4][(η 5-C 5Me 5)WS 3] under the presence of M′Cl 2 (M′ = Zn, Cd, Hg) in high concentrations were discussed.