Synthesis, Supramolecular Self-Organization, and Thermal Behavior of Gold(III)-Thallium(III) Heteronuclear Complexes ([Au{S2CN(CH3)(2)}(2)][TlCl4])(2) and ([Au{S2CN(C2H5)(2)}(2)][TlCl4]) (n)

摘要

The interaction of polymeric thallium(I) dimethyl- and diethyldithiocarbamates with [AuCl4](-) in 2 M HCl has been studied. Heteropolynuclear complexes ([Au{S2CN(CH3)(2)}(2)][TlCl4])(2) (I) and ([Au{S2CN(C2H5)(2)}(2)][TlCl4]) (n) (II) have been preparatively isolated from chemisorption systems [Tl-2{S2CNR2}2] (n) -Au3+/2 M HCl (R = CH3, C2H5). These compounds have been characterized by C-13 CP/MAS NMR, and their crystal and supramolecular structures have been determined by X-ray crystallography. Basic structural units of compounds I and II are square-planar [Au{S2CNR2}(2)](+) cations (with S,S'- bidentate coordination of two Dtc ligands to the gold atom) and distorted tetrahedral [TlCl4]-anions. In supramolecular self-organization, the decisive role is played by relatively weak secondary interactions Aua <-S and Aua <-Cl. With the use of simultaneous thermal analysis, the thermal behavior of I and II have been studied, which enabled the elucidation of temperature-induced transformations and identification of TlCl and reduced gold among the thermolysis products.