Natural Abundance 15N and 13C CP/MAS NMR of Dialkyldithiocarbamate Compounds with Ni(II) and Zn(II)
Different symmetrically substituted and cyclic dialkydithiocarbamate (R=CH3, C2H5, C3H7, i-C3H7, C4H9, i-C4H9 and R2=(CH2)5, (CH2)6, (CH2)4O) compounds, such as tetraalkylthiuram disulfides, mononuclear nickel(II), binuclear zinc(II) and heteropolynuclear complexes and their adducts (both non-solvated and solvated forms) with planar and non-planar N-donor organic bases, have been prepared and studied by means of natural abundance 13C and 15N CP/MAS NMR spectroscopy. Useful correlations between molecular structures and 13C and 15N chemical shifts in these compounds have been established and assignments to carbon and nitrogen sites in resolved molecular structures have been suggested. A combination of the mesomeric effect of dithiocarbamate groups and the (+)inductive effect of alkyl substituents at the nitrogen atoms has been discussed in interpretations of 13C and 15N chemical shifts of the studied compounds. A high sensitivity of 15N chemical shift to the subtle structural differences of both dithiocarbamate groups and N-donor molecules has been revealed. Several remarkable cases of conformational isomerism have been recognized for both dithiocarbamate complexes and their adducts.
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