Dithiocarbamato-Chlorido Gold(III) Complexes [Au(S2CNPr2)2][AuCl4] and [Au(S2CNPr2)Cl2]: Structural Organization, Interconversions in Solution, and Thermal Behavior

The interaction of freshly precipitated binuclear [Zn2(S2CNPr2)4] with an H[AuCl4]/2 M HCl solution has afforded the dipropyldithiocarbamato-chlorido complexes of gold(III): ionic [Au(S2CNPr2)2][AuCl4] (1) and molecular [Au(S2CNPr2)Cl2] (2) ones, the structural organization of which has been elucidated using single-crystal XRD. Supramolecular self-assembly of the complexes involving multiple non-covalent interactions (secondary bonds Au···S, S···Cl and non-classical hydrogen bonds C–H···Cl) leads to the formation of 2D pseudo-polymeric layers. In a solution, ionic complex 1 tends to undergo gradual spontaneous transformation into molecular compound 2. The only final product of thermal decomposition of the considered compounds is microcrystalline elemental gold.