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Crystal structure, solid-state 13C and 15N NMR characterisation, chemisorption activity and thermal behaviour of new mercury(II) dipropyldithiocarbamate : Binuclear, pseudo-binuclear and heteronuclear complexes of [Hg2(PrDtc)4], [Hg(PrDtc)2]2 and [Au(PrDtc)2]2[Hg2Cl6]. / Rodina, Tatyana A.; Loseva, Olga V.; Smolentsev, Anton I. и др.
в: Inorganica Chimica Acta, Том 508, 119630, 01.08.2020.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Crystal structure, solid-state 13C and 15N NMR characterisation, chemisorption activity and thermal behaviour of new mercury(II) dipropyldithiocarbamate
T2 - Binuclear, pseudo-binuclear and heteronuclear complexes of [Hg2(PrDtc)4], [Hg(PrDtc)2]2 and [Au(PrDtc)2]2[Hg2Cl6]
AU - Rodina, Tatyana A.
AU - Loseva, Olga V.
AU - Smolentsev, Anton I.
AU - Antzutkin, Oleg N.
AU - Ivanov, Alexander V.
N1 - Publisher Copyright: © 2020
PY - 2020/8/1
Y1 - 2020/8/1
N2 - Two polymorphs of a new mercury(II) N,N-dipropyldithiocarbamate represented by centrosymmetric binuclear and pseudo-binuclear molecules, [Hg2(PrDtc)4] (1) and [Hg(PrDtc)2]2 (2), have been isolated, identified using heteronuclear (13C, 15N) CP-MAS NMR and structurally characterised by single-crystal X-ray diffraction analysis. There are two pairs of inequivalent PrDtc ligands playing either terminal chelating or tridentate bridging structural functions in the former compound; while the latter complex comprises two pairs of structurally inequivalent chelating PrDtc ligands. The reaction of freshly precipitated mercury(II) N,N-dipropyldithiocarbamate (HgPrDtc) with a [AuCl4]−/2 M HCl solution results in the formation of the ionic complex [Au(PrDtc)2]2[Hg2Cl6] (3). There are two inequivalent centrosymmetric cations, [Au(PrDtc)2]+ (‘A’ and ‘B’), and a binuclear centrosymmetric anion, [Hg2Cl6]2− in the structure of 3. In the cationic part of the complex, each of the gold(III) cations has two pairs of the relatively weak inequivalent secondary Au···S bonds with two neighbours, therefore forming linear supramolecular cationic chains (⋯‘A’⋯‘B’⋯‘A’⋯‘B’⋯)n. To study the thermal behaviour of the compounds, simultaneous thermal analysis was also performed. The formation of HgS and reduced elemental gold was established during the thermolysis of 1/2 and 3, respectively.
AB - Two polymorphs of a new mercury(II) N,N-dipropyldithiocarbamate represented by centrosymmetric binuclear and pseudo-binuclear molecules, [Hg2(PrDtc)4] (1) and [Hg(PrDtc)2]2 (2), have been isolated, identified using heteronuclear (13C, 15N) CP-MAS NMR and structurally characterised by single-crystal X-ray diffraction analysis. There are two pairs of inequivalent PrDtc ligands playing either terminal chelating or tridentate bridging structural functions in the former compound; while the latter complex comprises two pairs of structurally inequivalent chelating PrDtc ligands. The reaction of freshly precipitated mercury(II) N,N-dipropyldithiocarbamate (HgPrDtc) with a [AuCl4]−/2 M HCl solution results in the formation of the ionic complex [Au(PrDtc)2]2[Hg2Cl6] (3). There are two inequivalent centrosymmetric cations, [Au(PrDtc)2]+ (‘A’ and ‘B’), and a binuclear centrosymmetric anion, [Hg2Cl6]2− in the structure of 3. In the cationic part of the complex, each of the gold(III) cations has two pairs of the relatively weak inequivalent secondary Au···S bonds with two neighbours, therefore forming linear supramolecular cationic chains (⋯‘A’⋯‘B’⋯‘A’⋯‘B’⋯)n. To study the thermal behaviour of the compounds, simultaneous thermal analysis was also performed. The formation of HgS and reduced elemental gold was established during the thermolysis of 1/2 and 3, respectively.
KW - Chemisorption activity
KW - Heteronuclear (C, N) CP-MAS NMR spectroscopy
KW - Ionic double gold(III)-mercury(II) compound
KW - Mercury(II) dipropyldithiocarbamate's binuclear and pseudo-binuclear polymorphs
KW - Secondary (Hg⋯S, Au⋯S) interactions
KW - Thermal behavior
KW - CENTER-DOT-S
KW - MOLECULAR-STRUCTURE
KW - CHEMICAL-SHIFTS
KW - X-RAY-DIFFRACTION
KW - HG(II) COMPLEXES
KW - SELF-ORGANIZATION
KW - Secondary (Hg center dot center dot center dot S, Au center dot center dot center dot S) interactions
KW - SUPRAMOLECULAR STRUCTURE
KW - Heteronuclear (C-13, N-15) CP-MAS NMR spectroscopy
KW - CP/MAS C-13
KW - CYCLIC DITHIOCARBAMATE LIGANDS
KW - MAS NMR
UR - http://www.scopus.com/inward/record.url?scp=85082728300&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2020.119630
DO - 10.1016/j.ica.2020.119630
M3 - Article
AN - SCOPUS:85082728300
VL - 508
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
M1 - 119630
ER -
ID: 23950102