Alkylation of tetrathiotungstate anions: crystal structures of the alkylthiolatotrithiotungstate complexes [PPh₄]₂[WS₃(S ⁿ Pr)][WS₃(S ⁿ Bu)]·½C₆H₆ and [PPh₄][WS₃(SCH₂C₆H₄CH₂Cl-4)]

Abstract

The reaction of [PPh4]2[WS4] in CH3CN with excess n-propylbromide or n-butylbromide gave alkylthiolatotrithiotungstate complexes, [PPh4][WS3(SR)] (1: R=n-propyl; 2: R=n-butyl). The analogous reaction with 1-bromomethyl-4-chloromethyl-benzene afforded a benzylthiolatotrithiotungstate complex, [PPh4][WS3(SCH2C6 H4CH2Cl-4)] (3), whereas the reaction with 1,4-bis-bromomethyl-benzene led to isolation of a dinuclear complex [PPh4]2[WS3(μ-SCH2C6H4CH2S)WS3] (4). Complexes 1–4 were characterized spectroscopically and the crystal structures of 1/2·½C6H6 and 3 have been determined by X-ray diffraction.