Complexation in a 5-acylpyrimidine-4-thione-aliphatic diamine-metal(II) chloride system (M = Ni or Co). The molecular structure of fac-tris(5-acetyl-2,4-dimethylpyrimidine-6-thiolato)cobalt(III)статья

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[1] Complexation in a 5-acylpyrimidine-4-thione-aliphatic diamine-metal(ii) chloride system (m = ni or co). the molecular structure of fac-tris(5-acetyl-2,4-dimethylpyrimidine-6-thiolato)cobalt(iii) / E. K. Beloglazkina, A. A. Chizhevskii, V. N. Nuriev et al. // Russian Chemical Bulletin. — 2005. — Vol. 54, no. 12. — P. 2757–2770. The reactions of 5-acylpyrimidine-4-thiones with aliphatic diamines in the presence of Ni-II and Co-II salts were studied. New Ni-II and Co-II complexes with ligands of the pyrimidinethione series were synthesized. The results of the reactions of 5-acetyl-6-methyl-2-phenylpyrimidine-4-thione and 5-acetyl-2,6-dimethylpyrimidine-4-thione with ethylenediamine or 1,3-diaminopropane in the presence of NiCl(2)(.)6H(2)O or CoCl(2)(.)6H(2)O depend on (1) the nature of the substituent at position 2 of the pyrimidine ring, (2) the length of the polymethylene bridge between the nitrogen atoms in the diamine molecule, (3) the nature of complex-forming metal, and (4) the pyrimidinethione: diamine ratio. The resulting complexes were studied by electrochemical methods. The mechanism of electrooxidation and electroreduction of 5-acylpyrimidine-2-thiones and related nickel and cobalt complexes was proposed. The structures of the complexes were investigated by NMR, UV-Vis spectroscopy, and IR spectroscopy and mass spectrometry. The molecular structure of fac-tris(5-acetyl-2,4-dimethylpyrimidine-6-thiolato)cobalt(III) was established by X-ray diffraction. According to semiempirical quantum-chemical calculations by the PM3(tm) method, both the highest occupied and lowest unoccupied molecular orbitals in the molecules of the compounds under study have a pi symmetry and are localized predominantly on the ligand fragments. [ DOI ]

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