Adducts of Zinc and Copper(II)Dimethyl-and Diethyldithiocarbamates with Piperidine:Synthesis,EPR,Solid-State Natural Abundance ~(13)C and ~(15)N CP/MAS NMR and Single-Crystal X-Ray Diffraction Studies

摘要

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 ~(63)Cu;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 ~(13)C and ~(15)N 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 computer-assisted 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 ~(13)C and ~(15)N 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.