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Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n: Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer chains), and thermal behavior

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Abstract

Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn2{S2CN(C4H9)2}4] resulted in the formation of a polymeric heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complex ([Au{S2CN(C4H9)2}2]2[ZnCl4]) n (I), which was characterized by MAS 13C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S2CN(C4H9)2}2]+, with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl4]2– anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation–cationic chains (via pair non-valence secondary Au···S bonds): (···A···B···C···D···C···B···) n and (···F···G···H···I···J···K···) n . The discrete E, L, and M cations and the [ZnCl4]2– complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion.

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Authors and Affiliations

  1. Institute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences, Blagoveshchensk, 675000, Russia

    A. V. Ivanov & O. V. Loseva

  2. Amur State University, Blagoveshchensk, 675027, Russia

    T. A. Rodina

  3. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090, Russia

    A. I. Smolentsev

  4. Novosibirsk State University, Novosibirsk, 630090, Russia

    A. I. Smolentsev

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  1. A. V. Ivanov
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  2. O. V. Loseva
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  3. T. A. Rodina
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  4. A. I. Smolentsev
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Correspondence to A. V. Ivanov.

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Original Russian Text © A.V. Ivanov, O.V. Loseva, T.A. Rodina, A.I. Smolentsev, 2017, published in Koordinatsionnaya Khimiya, 2017, Vol. 43, No. 8, pp. 482–495.

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Ivanov, A.V., Loseva, O.V., Rodina, T.A. et al. Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n: Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer chains), and thermal behavior. Russ J Coord Chem 43, 512–525 (2017). https://doi.org/10.1134/S1070328417080036

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  • DOI: https://doi.org/10.1134/S1070328417080036

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