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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

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Abstract

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.

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Authors and Affiliations

  1. Russian Academy of Sciences, Amur Integrated Research Institute, Far East Division, Relochnyi per. 1, Blagoveshchensk, 675000, Russia

    A. V. Ivanov & I. A. Lutsenko

  2. Luleå University of Technology, S-971 87, Luleå, Sweden

    W. Forsling

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  1. A. V. Ivanov
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  2. I. A. Lutsenko
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  3. W. Forsling
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Ivanov, A.V., Lutsenko, I.A. & Forsling, W. Bis(dimethyldithiocarbamato)(pyridine)zinc and -copper(II) and Their Benzene Solvates: EPR and Solid-State Natural Abundance (13C, 15N) CP/MAS NMR. Russian Journal of Coordination Chemistry 28, 57–63 (2002). https://doi.org/10.1023/A:1013720022120

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