Adducts of zinc and copper(II) dimethyland diethyldithiocarbamates with piperidine: Synthesis, EPR, solid-state natural abundance C-13 and N-15 CP/MAS NMR and single-crystal X-ray diffraction studies

作者：Ivanov A V^*; Zaeva A S; Gerasimenko A V; Rodina T A

来源：Russian Journal of Coordination Chemistry, 2008, 34(9): 688-698.

DOI：10.1134/S1070328408090108

Crystalline adducts of zinc and copper(II) dimethyl-and diethyldithiocarbamates with piperidine (Pip) of the general formula [M{NH(CH2)(5)}(S2CNR2)(2)] (M = Zn and Cu-63; R = CH3 and C2H5) were obtained. Their structures and spectroscopic characteristics were studied by X-ray diffraction analysis, EPR spectroscopy, and solid-state natural abundance C-13 and N-15 MAS NMR spectroscopy. The most substantial differences between the adducts of the formula [Zn{NH(CH2)(5)}(S2CNR2)(2)] (R = CH3 and C2H5) were found in the spatial orientations of the coordinated heterocycles and the geometries of the zinc polyhedra. The individual character of the EPR spectra of magnetically diluted isotope-substituted copper(II) adducts was determined by computerassisted modeling. The adducts of copper(II) and zinc dimethyldithiocarbamates proved to exist as two isomers. The coordination polyhedra of copper(II) and zinc are intermediate between a tetragonal pyramid (TP) and a trigonal bipyramid (TBP). The contributions from the TBP/TP components to the coordination polyhedra were quantitatively estimated from X-ray diffraction data. The C-13 and N-15 NMR signals were assigned to the positions of the atoms of the =NC(S)S- groups in the resolved (according to X-ray diffraction data) molecular structures of the adducts.

• 出版日期2008-9