Abstract
The capability of silver(I) cyclo-hexamethylenedithiocarbamate to concentrate gold(III) from solutions characterized by a high level of salinity (5.15 M NaCl) into the solid phase has been established. The double chloroform-solvated Au(III)–Ag(I) complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (I) was preparatively isolated as an individual form of binding of [AuCl4]– anions. The composition of the ionic structural units of compound I indicates that gold(III) binding from a solution to the solid phase is accompanied by the complete redistribution of the HmDtc ligands between the coordination spheres of Ag(I) and Au(III). Complex I characterized by IR spectroscopy, simultaneous thermal analysis, and X-ray structure analysis (CIF file CCDC no. 2051654) exhibits the supramolecular structure containing two oppositely charged pseudo-polymeric subsystems. Complex cations [Au{S2CN(CH2)6}2]+ and anions [AgCl2]– (in a ratio of 2 : 1) form a complicatedly organized cation-anionic pseudo-polymeric ribbon ({[Au(HmDtc)2]⋅⋅⋅[AgCl2]⋅⋅⋅[Au(HmDtc)2]}+)n due to secondary interactions Ag⋅⋅⋅S (3.2613 Å) and Au⋅⋅⋅Cl (3.2765 Å). The pseudo-polymeric ribbon consists of two rows of cations and a row of anions. The outer-sphere chloride ions combine the solvate chloroform molecules by two equivalent hydrogen bonds Cl⋅⋅⋅H–C yielding anion-molecular triads [Cl3CH⋅⋅⋅Cl⋅⋅⋅HCCl3]–, which are involved in the formation of the supramolecular ribbon due to the secondary Cl⋅⋅⋅Cl interactions (3.4058 Å) between the nonequivalent chlorine atoms of the nearest solvate molecules. The study of the thermal behavior of complex I makes it possible to determine the character of thermolysis and conditions for the quantitative regeneration of bound gold.
Highlights
Silver(I) dithiocarbamate (Dtc) complexes are convenient precursors for the preparation of both acanthite (α-Ag2S) films and nanopowders [1,2,3,4] and Janus nanoparticles Ag2S/Ag0 [5, 6], which are of practical interest for microelectronics
Since Ag2S is characterized by low toxicity and high stability in biological media, it is promising to use it in medicine for manufacturing biocompatible nanoprobes [7, 8]
It is noteworthy that a low toxicity of silver against cells of mammals compared to other metals is combined in a unique manner with a high toxicity against microorganisms [9]
Summary
Silver(I) dithiocarbamate (Dtc) complexes are convenient precursors for the preparation of both acanthite (α-Ag2S) films and nanopowders [1,2,3,4] and Janus nanoparticles Ag2S/Ag0 (including a combination of the metal and metal sulfide) [5, 6], which are of practical interest for microelectronics. The strong interaction of vibrations of the C–H, C–C, and C–N bonds in the HmDtc ligands predetermines a complicated IR spectral pattern of complex I and substance Ia. when analyzing the spectrum, we used the IR spectral data for the initial [Ag6{S2CN(CH2)6}6] cluster [17], sodium cyclo-hexamethylenedithiocarbamate dihydrate Na{S2CN(CH2)6}·2H2O [21], hexamethyleneimine C6H12NH [22], cycloheptane C7H14 [23], and chloroform СНCl3.1 The IR spectra of compounds I/Ia exhibit absorption bands at 2926/2920 and 2844/ 2849 cm–1 due to stretching vibrations νas(СН2) and νs(СН2), respectively.
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