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DOUBLE GOLD(III)–ZINC(II) DI-ISO-BUTYLDITHIOCARBAMATO- CHLORIDO COMPLEXES OF THE COMPOSITION [Au(S2CNR2)2]2[Zn2Cl6] AND [Au(S2CNR2)2][Zn(S2CNR2)Cl2]: SYNTHESIS, STRUCTURAL ORGANIZATION, 13C CP-MAS NMR, AND THERMAL BEHAVIOR

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Abstract

The interaction of zinc(II) di-iso-butyldithiocarbamate with [AuCl4]— anions in 2M HCl is studied. The result of chemisorption binding of gold(III) from a solution to the solid phase is the formation of double ionic complexes of the compositions [Au{S2CN(iso-C4H9)2}2]2[Zn2Cl6] (1) and [Au{S2CN(iso-C4H9)2}2][Zn{S2CN(iso-C4H9)2}Cl2] (2). The chemical identification of preparatively isolated crystalline compounds was performed by 13C CP-MAS NMR spectroscopy. According to single crystal X-ray diffraction data, structural units of complex 1 are a binuclear zinc anion and non-equivalent complex [Au{S2CN(iso-C4H9)2}2]+ cations: centrosymmetric A with the Au(1) atom and С – Au(3) and non-centrosymmetric В – Au(2). With the participation of secondary Cl⋯S bonds (3.2407 Å and 3.2756 Å), В cations and anions form supramolecular ionic pairs. The structure of 2 in turn involves the centrosymmetric gold(III) cation whose counterion is a mixed-ligand dithiocarbamato-chlorido anion of zinc(II). Pairs of non-equivalent secondary Cl⋯S bonds (3.2337 Å and 3.3151 Å) combine the ionic structural units of 2 into zigzag-like pseudo-polymeric chains along which the alternation of complex cations and anions is noted. Thermolysis of complexes in cationic and anionic parts is accompanied by the quantitative regeneration of bound gold along with the formation of ZnCl2 and ZnS.

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Notes

  1. *Among all zinc(II) dithiocarbamates that have been structurally characterized so far [30], the di-iso-butyldithiocarbamate complex has a unique character of constructing the crystal lattice with an alternation of monomeric [Zn{S2CN(iso-C4H9)2}2] and dimeric [Zn2{S2CN(iso-C4H9)2}4] molecular forms present in the 1:1 ratio [31].

  2. *Apart from non-centrosymmetric anions [40, 41], the examples of centrosymmetric [Zn2Cl6]2– anions have also been reported [42].

  3. **Examples of heteroleptic complexes simultaneously containing R2NC(S)S– and Cl– ligands have been known for zinc(II) [43-45], however, all these compounds are neutral and for the coordinative saturation of the central metal atom they additionally attach molecules of N,N′-donor bases (1,10-phenanthroline or 2,2′-bipyridine) are. Therefore, the structural analogues of the discussed anion are mainly copper(II) complexes of the composition [Cu(EtDtc)Cl2]– [46].

  4. * The formation of metal sulfides during thermolysis of complexes with sulfur-containing ligands is substantiated in [51] from the standpoint of thermodynamics.

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Authors and Affiliations

  1. Amur State University, Blagoveshchensk, Russia

    T. A. Rodina

  2. Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences, Blagoveshchensk, Russia

    O. V. Loseva & A. V. Ivanov

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Rodina, T.A., Loseva, O.V. & Ivanov, A.V. DOUBLE GOLD(III)–ZINC(II) DI-ISO-BUTYLDITHIOCARBAMATO- CHLORIDO COMPLEXES OF THE COMPOSITION [Au(S2CNR2)2]2[Zn2Cl6] AND [Au(S2CNR2)2][Zn(S2CNR2)Cl2]: SYNTHESIS, STRUCTURAL ORGANIZATION, 13C CP-MAS NMR, AND THERMAL BEHAVIOR. J Struct Chem 62, 123–136 (2021). https://doi.org/10.1134/S0022476621010157

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