First Cobalt Complexes With Methyl Pyruvate Semi/Thiosemicarbazone - Synthesis, Physicochemical And Structural Characterization

In the reaction of acetone solutions of CoX2 center dot nH(2)O (X = Cl, Br) with methyl pyruvate semi/thiosemicarbazone (Hmps, Hmpt) the first Co(II) complexes with these ligands, i.e., [Co(Hmps)(H2O)X-2] (X = Cl (1), Br (2)), [Co(Hmpt)(2)][CoCl4]center dot 2H(2)O (3) and [Co(Hmpt)(2)]Br-2 center dot Me2CO (4) were obtained. Complexes 1 and 2 represent the first examples of metal complexes of Hmps. All the obtained compounds were characterized by elemental analysis, conductometry, magnetic measurements, and IR spectra, and for complexes 2-4, single crystal X-ray diffraction analysis was also performed. The effective magnetic moments were close to the upper limit (5 mu(B)) for complexes 1 and 2, and close to the lower limit (4.4 mu(B)) for complexes 3 and 4, and as such are characteristic for high-spin Co(II) complexes. Structural analysis showed that both ligands coordinate in a neutral form in a tridentate manner, via the ester oxygen, imine nitrogen and the oxygen atom of the ureido (Hmps), or the sulfur atom of the thioureido group (Hmpt). The central metal atoms are situated in a deformed octahedral coordination environment. Complex 2 has cis-Br configuration, while complexes 3 and 4 have mer- configuration.