Adducts of diethyldithiocarbamate complexes of zinc(II) and copper(II) with piperidine [M(Pip)(Edtc)(2)] and their solvated forms [M(Pip)(Edtc)(2)] center dot L (L = C6H6, C5H5N, C4H9NO): Synthesis, EPR and solid-state (C-13, N-15) CP/MAS NMR studies

Crystal adducts of diethyldithiocarbamate complexes of zinc(II) and copper( II) with piperidine (Pip) were synthesized, and their solvated forms with t he outer-sphere molecules of benzene, pyridine (Py), and morpholine (Mf) we re obtained. Adducts with composition [M(Pip)(Edtc)(2)] . L (L = Py, Mf) we re shown to he able, in principle, to give solvated isomers IM(L)(Edtc)(2)] . Pip with the Pip molecule arranged in the outer sphere. The composition, structure, and properties of the obtained adducts were studied by EPR, hig h-resolution solid-state C-13, N-15 NMR spectroscopy. Solvation of all thre e adducts with Pip, Mf, and Py was found to result in a substantial increas e in the contribution of the trigonal-bipyramidal component to the geometry of a copper coordination pentahedron. In addition, for adducts with Mf and Py, a structural unification of two isomeric forms was observed at the mol ecular level to yield a qualitatively new (rather than intermediate) state. It was shown that in all solvated forms of the copper(II) adducts, the met al polyhedron is mainly a trigonal bipyramid, while the square-pyramidal co ntribution is insignificant. Results of(C-13, N-15) NMR studies revealed a structural inequivalence of the Edtc(-) ligands in the zinc adducts under i nvestigation.