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Year 2005, Month 12 (Section Full Articles, Page 2771)

Synthesis and electrochemical study of complexes of 2-methylthio-5-(pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-ones with transition metals (Co, Ni, and Cu). Molecular structures of CuIIL1Cl2 (L1 is (5Z )-2-methylthio-3-phenyl-5-(α-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one) and CoIIL2Cl2 (L2 is (5Z )-3-methyl-2-methylthio-5-(α-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one)

E. K. Beloglazkina, S. Z. Vatsadze, A. G. Majouga, N. A. Frolova, R. B. Romashkina, N. V. Zyk, A. A. Moiseeva, and K. P. Butin†

New transition metal (NiII, CoII, and CuII) complexes with 2-methylthio-5-(pyridyl- methylidene)-3,5-dihydro-4H-imidazol-4-ones were synthesized by the reaction of 5-(α-, β-, or γ-)pyridyl-substituted 2-methylthio-3,5-dihydro-4H-imidazol-4-ones with MCl2•nH2O. In the complexes with α-Py-substituted ligands, the metal atom has a tetrahedral coordination environment and is coordinated by the nitrogen atoms of the pyridine and thiohydantoin rings and two chloride anions. The results of electronic spectroscopy and magnetic susceptibility-measurements suggest that the complexes with the β- and γ-Py-substituted ligands have polymeric structures, and the metal atoms in these complexes are in an octahedral environment.-The molecular and crystal structures of CuIIL1Cl2 (L1 is (5Z)-2-methylthio-3-phenyl-5-(α-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one) and CoIIL2Cl2 (L2 is (5Z )-3-me-thyl-2-methylthio-5-(α-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one) were established by X-ray diffraction. Semiempirical quantum-chemical calculations were performed for 2-methylthio-5-(pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-ones. The complexes, starting ligands, and metal chlorides were studied electrochemically. The mechanism of electrooxidation and electroreduction of 2-methylthio-5-(pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-ones and their cobalt, nickel, and copper complexes was proposed.

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