Binding of Gold(III) from Solutions with Thallium(I) Dibutyldithiocarbamate: Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Complex ([Au{S2CN(C4H9)2}2][TlCl4])n

Resumo

The binding of gold(III) from solution in a 2 M HCl with thallium(I) dibutyl dithiocarbamate leads to the formation of ion-polymeric complex ([Au{S₂CN(C₄H₉)₂}₂][TlCl₄])_n, which was studied by (¹³С, ¹⁵N) MAS NMR spectroscopy and X-ray diffraction analysis. In the complex comprising the nonequivalent cations [Au{S₂CN(C₄H₉)₂}₂]⁺ (A and B) and anions [TlCl₄]^–, the supramolecular self-assembly is provided by secondary bonds Au···S and S···Cl. The former are involved in the formation of isomeric binuclear cations [А···А] and [В···В] that build the (···[А···А]···[В···В]···)_n polymeric chain; the latter selectively combine the thallium(III) anions and the dimeric cations. Thermolysis of the complex is accompanied by gold recovery and release of TlCl.