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Bis(dimethyldithiocarbamato)(pyridine)zinc and -copper(II) and Their Benzene Solvates: EPR and Solid-State Natural Abundance (13C, 15N) CP/MAS NMR
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Sustainable Process Engineering.
Russian Adademy of Sciences.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Sustainable Process Engineering.
2002 (English)In: Russian journal of coordination chemistry, ISSN 1070-3284, E-ISSN 1608-3318, Vol. 28, no 1, p. 57-63Article in journal (Refereed) Published
Abstract [en]

Adducts of bis(dimethyldithiocarbamato)zinc and -copper(II) complexes with pyridine, [M(Py)(Mdtc)2], and their benzene solvates [M(Py)(Mdtc)2] · 0.5C6H6 were synthesized. The electron paramagnetic resonance method and solid-state 13C and 15N CP/MAS NMR spectroscopy were used to perform a comparative study of the compounds obtained. The EPR data showed that the geometry of Cu(II) coordination polyhedra both in the adduct itself [Cu(Py)(Mdtc)2], and in its solvate, [Cu(Py)(Mdtc)2] · 0.5C6H6 is intermediate between a square pyramid (SP) and a trigonal bipyramid (TBP), the contribution from the latter being dominant (75%) in [Cu(Py)(Mdtc)2]. In the solvated adduct [Cu(Py)(Mdtc)2] · 0.5C6H6, the copper(II) polyhedron is distorted to form an SP-enriched structure (the contribution from TBP is reduced to 55%). It was found NMR data that [Zn(Py)(Mdtc)2] exists in a single high-symmetry molecular form. Coordinated pyridine molecule shows molecular motion about the Zn-N bond. The solvation of the adduct results in structural nonequivalence of the Mdtc-ligands in [Zn(Py)(Mdtc)2] · 0.5C6H6. Signals in the 15N NMR spectra were assigned to the structural positions of the atoms in the previously described molecular structure of a solvated adduct. It was found that the heterogeneous reaction of adduct formation during the absorption of pyridine from the gas phase by polycrystalline [Zn2(Mdtc)4] species is accompanied by the dissociation of binuclear molecules.

Place, publisher, year, edition, pages
2002. Vol. 28, no 1, p. 57-63
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
URN: urn:nbn:se:ltu:diva-4036DOI: 10.1023/A:1013720022120Local ID: 1e554ec0-dcff-11db-9cae-000ea68e967bOAI: oai:DiVA.org:ltu-4036DiVA: diva2:976898
Note
Validerad; 2002; 20070328 (bajo)Available from: 2016-09-29 Created: 2016-09-29 Last updated: 2017-11-24Bibliographically approved

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