TY - JOUR

T1 - Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n

T2 - Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer chains), and thermal behavior

AU - Ivanov, A. V.

AU - Loseva, O. V.

AU - Rodina, T. A.

AU - Smolentsev, A. I.

PY - 2017/8/1

Y1 - 2017/8/1

N2 - 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 AuS bonds): (ABCDCB)n and (FGHIJK)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.

AB - 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 AuS bonds): (ABCDCB)n and (FGHIJK)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.

KW - CMAS NMR

KW - crystal and supramolecular structures

KW - gold species extracted from solutions

KW - heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complexes

KW - simultaneous thermal analysis

KW - X-ray diffraction

KW - zinc dialkyl dithiocarbamates

KW - SYSTEM

KW - HETEROPOLYNUCLEAR COMPLEX

KW - MOLECULAR-STRUCTURE

KW - CP/MAS-NMR

KW - ZINC-COMPLEXES

KW - N-15

KW - C-13 MAS NMR

KW - HCL

KW - DITHIOCARBAMATE

KW - C-13

KW - RAY CRYSTAL-STRUCTURES

KW - heteronuclear gold(III)-zinc(II) dithiocarbamato-chlorido complexes

UR - http://www.scopus.com/inward/record.url?scp=85027857392&partnerID=8YFLogxK

U2 - 10.1134/S1070328417080036

DO - 10.1134/S1070328417080036

M3 - Article

AN - SCOPUS:85027857392

VL - 43

SP - 512

EP - 525

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 8

ER -