Abstract
The thermodynamic and geometric parameters of asymmetric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NSSN)-coordination of the ligand donor sites that can form upon the complexation involving hexacyanoferrates(II) of the above metal ions, dithiooxamide H2N-C(=S)-C(=S)-NH2, thiosemicarbazide H2N-HN-C(=S)-NH2, and formaldehyde H2C(=O) in gelatin-immobilized matrices have been calculated by the OPBE/TZVP nonhybrid DFT method. The bond lengths and bond and non-bonded angles in the complexes are reported. It has been shown that these complexes can be divided into two categories. The complexes of the first category are characterized by rather well-pronounced non-coplanarity of the MN2S2 chelate core, the N2S2 moiety, and one of the five-membered chelate rings, while the other two chelate rings are severely non-coplanar (the Mn(II), Fe(II), and Zn(II) chelates). The complexes of the second category are characterized by perfect or nearly perfect coplanarity of the MN2S2 chelate core, the N2S2 moiety, and one of the five-membered chelate rings and moderate non-coplanary of the second five-membered chelate ring, while the six-membered chelate ring is severely non-coplanar (the Ni(II) chelate). The Co(II) and Cu(II) chelates occupy the intermediate position (but closer to the second category).
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Original Russian Text © O.V. Mikhailov, D.V. Chachkov, 2014, published in Zhurnal Neorganicheskoi Khimii, 2014, Vol. 59, No. 12, pp. 1719–1726.
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Mikhailov, O.V., Chachkov, D.V. Molecular structures and stability of isomeric asymmetric (565)macrotricyclic chelates of 3d metals in the M(II)-dithiooxamide-thiosemicarbazide-formaldehyde systems according to DFT calculations. Russ. J. Inorg. Chem. 59, 1472–1479 (2014). https://doi.org/10.1134/S0036023614120171
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DOI: https://doi.org/10.1134/S0036023614120171