Heterovalent Gold(I,III) complex ([Au{S2CN(CH2)6}2]3[AuCl2]2Cl])n: Synthesis, structure, and 13C MAS NMR

Abstract

The reaction of the freshly precipitated oxovanadium(IV) cyclo-hexamethylenedithiocarbamate complex with [AuCl₄]^– anions in a 2 M HCl solution is studied. The water-soluble heterovalent complex ([Au{S₂CN(CH₂)₆}₂]₃[AuCl₂]₂Cl])_n (I) is formed due to the redox reaction. According to the X-ray diffraction data, structure I contains two species of complex cations [Au{S₂CN(CH₂)₆}₂]⁺ as conformers performing different structural functions: non-centrosymmetric cations and centrosymmetric cation B in a ratio of 2: 1. Cations A form centrosymmetric dimers [Au{₂S₂CN(CH₂)₆}₄]²⁺ due to pairs of symmetrical secondary bonds Au…S. The aurophilic Au…Au and secondary Au…S interactions that occur between the complex cations and anions in crystal result in the formation of a polymer network.