Syntheses and structural characterizations of a series of Mo(W)–Cu–S compounds of bidentate dialkyldithiocarbamate ligands. Crystal structure of [NEt4]2[Mo2Cu5S6O2(Me2NCS2)3]

Abstract

The complex [NEt₄]₂[Mo₂Cu₅S₆O₂(Me₂NCS₂)₃] has been prepared by the reaction of CuCl, Na[S₂CNMe₂],NEt₄Br, and [NH₄]₂[MoS₂O₂] in dimethylformamide solution. It crystallizes in the orthogonal space group Pnma with a= 23.373(3), b= 17.202(3), c= 12.474(4)Å, and Z= 4. The Mo₂Cu₅S₆O₂ framework in the anion consists of two defective cubane-like units OMoS₃Cu₂ and OMoS₃Cu₃ linked through two weak Cu–S bonds and bridged by two Me₂NCS₂ ligands. The synthesis of the series of compounds [NEt₄]₂[M₂Cu₅S₈(Me₂NCS₂)₃], [PPh₄]₂[M₂Cu₅S₆O₂(Et₂NCS₂)₃](M = Mo or W), and [NEt₄]₂[MoCu₃S₄(Et₂NCS₂)₃] are reported. Their structures are discussed together with their ¹H, ¹³C, and ⁹⁵Mo n.m.r. spectra in solution.