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Structural organization of mercury(II) and copper(II) dithiocarbamates from EPR and 13C and 15N MAS NMR spectra and X-ray diffraction analysis
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Sustainable Process Engineering.
Institute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences, Blagoveshchensk.
Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, 690022, Vladivostok.
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2008 (English)In: Russian journal of coordination chemistry, ISSN 1070-3284, E-ISSN 1608-3318, Vol. 34, no 1, p. 59-69Article in journal (Refereed) Published
Abstract [en]

The structures and spectroscopic properties of mononuclear and binuclear mercury(II) and copper(II) complexes with four dithiocarbamate ligands R 2NC(S)S- (R = CH3, C2H5, or iso-C3H7; R2 = (CH2)6) were studied by solid-state 13C and 15N CP/MAS NMR and EPR spectroscopy. Mercury(II) N,N-cyclohexamethylenedithiocarbamate [Hg 2{S2CN(CH2)6}4] was obtained and characterized in detail by X-ray diffraction analysis at 299 K. The binuclear molecule of the complex is centrosymmetric; the central tricyclic fragment [Hg2S4C2] is in the chair conformation. In the 13C and 15N NMR spectra, the signals were assigned to the dithiocarbamate ligands with different structural functions: bidentate chelating and combined (both chelating and bridging) ones. The differences between the isotropic 15N chemical shifts for the dialkyldithiocarbamate ligands were interpreted in terms of combination of the mesomeric effect of the =NC(S)S-groups and the inductive effect of the alkyl substituents. According to the EPR data, copper(II) in magnetically diluted systems is mainly found in heterobinuclear molecules [CuHg(S2CNR 2)4] and the geometry of the chromophores [CuS 5] approximates to a tetragonal pyramid.

Place, publisher, year, edition, pages
2008. Vol. 34, no 1, p. 59-69
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
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URN: urn:nbn:se:ltu:diva-8368DOI: 10.1007/s11173-008-1010-3Scopus ID: 2-s2.0-38849161384Local ID: 6e116be0-73a0-11dd-a60f-000ea68e967bOAI: oai:DiVA.org:ltu-8368DiVA, id: diva2:981260
Note
Validerad; 2008; 20080826 (ysko)Available from: 2016-09-29 Created: 2016-09-29 Last updated: 2018-07-10Bibliographically approved

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Ivanov, AlexanderGoryan, Alexander S.Antzutkin, OlegForsling, Willis

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