A comparative study of the structural organization of nickel(II) and copper(II) complexes with dialkyl-substituted and cyclic dithiocarbamate ligands by X-ray single-crystal diffraction, EPR, and CP/MAS C-13 and N-15 NMR

• X-ray single-crystal diffraction, EPR, and CP/MAS C-13 and N-15 NMR were used for studying the structures and spectral properties of nickel(II) and copper(II) dithiocarbamate complexes [M(S2CNR2)(2)] (R = CH3, C2H5, C3H7, i-C3H7 or R-2 = (CH2)(5), (CH2)(6), (CH2)(4)O). The [CUS4] chromophores in the lattice of nickel(II) complexes have, predominantly, a square-planar structure. The chromophore geometry is somewhat distorted only in bis(morpholinedithiocarbamato)copper(II). Differences in the N-15 NMR isotropic chemical shifts of dialkyldithiocarbamate ligands were interpreted in terms of a unified conceptual approach based on the concept of joint manifestation of the mesomeric effect of dithiocarbamate groups and the inductive effect of alkyl substituents. Experimental NMR (C-13, N-15) signals were assigned to the structural positions of atoms in allowed molecular structures. Refined structural data on [Ni{S2CN(C3H7)(2)}(2)] point to the occurrence of two types of structurally nonequivalent complex molecules; the [Ni(S2CN(CH2)6)2] complex is characterized by the intramolecular nonequivalence of dithiocarbamate ligands.

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NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

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Chemistry of Interfaces

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