Syntheses, supramolecular structures, and thermal behavior of heteronuclear gold(III)–mercury(II) dithiocarbamatochloride complexes [Au{S2CN(CH3)2}2]2[HgCl4] and ([Au{S2CN(C2H5)2}2]2[Hg2Cl6] · OC(CH3)2)n by 13C MAS NMR, ... View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2016-11

AUTHORS

O. V. Loseva, T. A. Rodina, A. I. Smolentsev, A. V. Ivanov

ABSTRACT

New heteronuclear gold(III)–mercury(II) compounds are synthesized by the chemisorption reaction of freshly precipitated mercury dimethyl (MeDtc) and diethyl dithiocarbamates (EtDtc) with [AuCl4]− anions in a medium of 2 M HCl. The crystals of complexes [Au{S2CN(CH3)2}2]2[HgCl4] (I) and ([Au{S2CN(C2H5)2}2]2[Hg2Cl6] • OC(CH3)2)n (II) are obtained from solutions in methanol and acetone, respectively. The crystal and supramolecular structures of the preparatively isolated compounds are determined by X-ray diffraction analysis (CIF files CCDC nos. 1452118 (I) and 1452119 (II)). The structure of ionic complex I is built of alternating binuclear [Au2{S2CN(CH3)2}4]2+ cations and [HgCl4]2− anions. A more complicated structure of compound II contains centrosymmetric isomeric [Au{S2CN(C2H5)2}2]+ cations (A and B) and centrosymmetric binuclear [Hg2Cl6]2− anions. The supramolecular structure of compound II is formed due to pairs of Au•••S secondary bonds between the adjacent gold(III) complex cations resulting in the formation of linear polymeric chains [•••A•••B•••]n (directed along the x crystallographic axis). Isomeric cations A and B are alternated along the chains. The character of thermolysis of the complexes is studied and the regeneration conditions of bound gold are revealed by the simultaneous thermal analysis data. The thermal destruction of compounds I and II occurs simultaneously at the cationic and anionic moieties of the compounds to reduce gold(III) accompanied by the release and subsequent sublimation of mercury(II) chloride. The final product of the thermal transformations of the complexes is reduced elemental gold. More... »

PAGES

719-729

References to SciGraph publications

  • 2015-10. Chemisorption binding of gold(III) from solutions with bismuth dipropyldithiocarbamate: Supramolecular self-assembly (role of the secondary Au…S and aurophilic interactions) and thermal behavior of the solvated heteropolynuclear ionic type complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9] • 0.5CO(CH3)2 • 0.5HCl)n in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
  • 2011-03. Gold(III) preconcentration from acid solutions by cadmium diisopropyldithiocarbamate: Gold(III)-binding species, supramolecular structure, and thermal properties of the heteropolynuclear complex ([Au{S2CN(iso-C3H7)2}2]2[CdCl4] · 1/2C3H6O)n in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2014-08. Structural organization and thermal behavior of the heteropolynuclear complex [Au2{S2CN(CH3)2}4][ZnCl4] and the heterovalent complex ([Au{S2CN(CH3)2}2][AuCl2])n obtained in the chemisorption system [Zn2{S2CN(CH3)2}4]-Au3+/2 M HCl in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2015-02. Chemisorption of gold(III) from solutions using thallium(I) diisobutyldithiocarbamate: Supramolecular structure and thermal behavior of the polymeric gold(III)-thallium(III) complex ([Au{S2CN(iso-C4H9)2}2][TlCl4])n in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
  • 2015-02. Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12])n with unusual geometry of bismuth(III) complex anion in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2016-06. 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 in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2016-02. Gold(III)–iron(III) heteropolynuclear complexes ([Au{S2CNR2}2][FeCl4])n (R = C4H9, iso-C4H9): Chemisorption synthesis, supramolecular self-organization, and thermal behavior in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
  • 2014-12. Interaction of binuclear zinc diethyldithiocarbamate with H[AuCl4]/2 M HCl: The preparation, supramolecular self-organization, and thermal behavior of the heteropolynuclear complex ([Au{S2CN(C2H5)2}2]2[ZnCl4] · 1/2CO(CH3)2 · 1/2CHCl3)n in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2013-05. Structural organization of dithiocarbamate heteropolynuclear gold(III)-cadmium complexes from X-ray crystallography and 113Cd MAS NMR spectroscopy data in JOURNAL OF STRUCTURAL CHEMISTRY
  • 2013-06. A fixation mode of gold(III) in the [Zn2{S2CN(iso-C3H7)2}4]-[AuCl4]−/2 M HCl chemisorption system: Supramolecular structure and thermal behavior of the heteropolynuclear complex ([H3O][Au3{S2CN(iso-C3H7)2}6][ZnCl4]2 · H2O)n in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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    34 schema:description New heteronuclear gold(III)–mercury(II) compounds are synthesized by the chemisorption reaction of freshly precipitated mercury dimethyl (MeDtc) and diethyl dithiocarbamates (EtDtc) with [AuCl4]− anions in a medium of 2 M HCl. The crystals of complexes [Au{S2CN(CH3)2}2]2[HgCl4] (I) and ([Au{S2CN(C2H5)2}2]2[Hg2Cl6] • OC(CH3)2)n (II) are obtained from solutions in methanol and acetone, respectively. The crystal and supramolecular structures of the preparatively isolated compounds are determined by X-ray diffraction analysis (CIF files CCDC nos. 1452118 (I) and 1452119 (II)). The structure of ionic complex I is built of alternating binuclear [Au2{S2CN(CH3)2}4]2+ cations and [HgCl4]2− anions. A more complicated structure of compound II contains centrosymmetric isomeric [Au{S2CN(C2H5)2}2]+ cations (A and B) and centrosymmetric binuclear [Hg2Cl6]2− anions. The supramolecular structure of compound II is formed due to pairs of Au•••S secondary bonds between the adjacent gold(III) complex cations resulting in the formation of linear polymeric chains [•••A•••B•••]n (directed along the x crystallographic axis). Isomeric cations A and B are alternated along the chains. The character of thermolysis of the complexes is studied and the regeneration conditions of bound gold are revealed by the simultaneous thermal analysis data. The thermal destruction of compounds I and II occurs simultaneously at the cationic and anionic moieties of the compounds to reduce gold(III) accompanied by the release and subsequent sublimation of mercury(II) chloride. The final product of the thermal transformations of the complexes is reduced elemental gold.
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