Binding of gold(III) with silver(I) dipropyldithiocarbamate: supramolecular self-assembly (role of secondary Au center dot center dot center dot S and Ag center dot center dot center dot S bonds) and thermal behavior of the ionic-polymer complex ([Au(S2CNPr2)(2)][AgCl2])(n)

摘要

The double ionic-polymer complex ([Au(S2CNPr2)(2)][AgCl2])(n) (1) was prepared as an individual fixation form of gold(III) from NaCl solutions with silver(I) dipropyldithiocarbamate and was characterized by single-crystal X-ray diffraction and C-13 magic-angle spinning (MAS) NMR spectroscopy. The structure of 1 comprises two nonequivalent centrosymmetric complex cations [Au(S2CNPr2)(2)](+) (A and B) and the discrete linear anion [AgCl2](-). Gold(III) cations are linked by pairs of unsymmetrical secondary Au center dot center dot center dot S bonds to form linear supramolecular chains (center dot center dot center dot A center dot center dot center dot B center dot center dot center dot)n. Neighboring cations are additionally linked by [AgCl2](-) anions via secondary Ag center dot center dot center dot S and Cl center dot center dot center dot S bonds, the anions being involved in the overall stabilization of the supramolecular structure. The cation-anion interactions lead to a distortion of the linear configuration of the [AgCl2](-) anion. The character of thermolysis of 1 accompanied by quantitative regeneration of bound Au and Ag was established by simultaneous thermal analysis.