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Synthesis, structure, and 13C and 31P CP/MAS NMR of crystalline modifications of the polynuclear thallium(I) O,O′-dicyclohexyl phosphorodithioate complex [Tl{S2P(O-cyclo-C6H11)2}]n
Amur State University, Blagoveshchensk, Russian Federation.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Sustainable Process Engineering.
Russian Academy of Sciences, Institute of Geology and Nature Management, Far East Division, Blagoveshchensk.
Amur State University, Blagoveshchensk, Russian Federation.
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2009 (English)In: Russian Journal of Inorganic Chemistry, ISSN 0036-0236, E-ISSN 1531-8613, Vol. 54, no 11, p. 1779-1788Article in journal (Refereed) Published
Abstract [en]

Two crystalline modifications (Ia and Ib) of the polynuclear thallium (I) O,O′-dicyclohexyl phosphorodithioate complex [Tl{S2P(O-cyclo-C6H11)2}] n have been synthesized and characterized by CP/MAS NMR (13C, 31P). From full 31P CP/MAS NMR spectra, the χ2 plots were constructed to calculate the 31P chemical shift anisotropy 31P - δaniso = (δzz - δiso) and asymmetry parameters η = (δ yy - δ xx )/(δ zz - δiso). The data obtained for the O,O′-dicyclohexyl phosphorodithioate (Dtph) groups (in both modifications) are evidence that the 31P chemical shift tensors are intermediate between rhombic and axially symmetric. However, whereas the rhombic component dominates for Ia, the tensor for Ib is close to axially symmetric (for δ zz < δ yy ≈ δ xx ). The same pattern of the MAS spectra corresponding to negative δaniso (δ zz < δ yy < δ xx ) points to a bridging or terminal/bridging coordination mode of the Dtph groups. X-ray crystallography shows that complex Ib has a polynuclear structure (of the chain polymer type). The chains are composed of alternating structurally nonequivalent noncentrosymmetric binuclear molecules [Tl2{S2P(O-cyclo-C6H11)2}2]. All Dtph ligands have the terminal/μ3-bridging coordination mode.

Place, publisher, year, edition, pages
2009. Vol. 54, no 11, p. 1779-1788
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
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URN: urn:nbn:se:ltu:diva-2396DOI: 10.1134/S0036023609110138ISI: 000271751600013Scopus ID: 2-s2.0-70450196185Local ID: 00213850-ddc0-11de-bae5-000ea68e967bOAI: oai:DiVA.org:ltu-2396DiVA, id: diva2:975248
Note
Validerad; 2009; 20091130 (ysko)Available from: 2016-09-29 Created: 2016-09-29 Last updated: 2023-09-05Bibliographically approved

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Ivanov, AlexanderAntzutkin, Oleg

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