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Comparative stability of isomeric (565)macrotricyclic chelates of 3d-elements formed in the systems M(II)-thiosemicarbazide-formaldehyde according to DFT B3LYP data

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Abstract

Comparative stability of three types of (565)macrotricyclic chelates of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with chelate nodes MN2S2 and MN4 have been analyzed by means of hybrid density functional method B3LYP with the 6-31G(d) basis set using GAUSSIAN-09 software. These chelates may potentially be formed in template interaction between gelatin-immobilized hexacyanoferrate(II) of respective metal ions M(II), thiosemicarbazide H2N-HN-C(=S)-NH2, and formaldehyde H2C=O. It has been demonstrated that for all M(II) considered, the complex with chelate nodes MN2S2 is more stable. Key structural parameters of the complexes (bond lengths, bond and torsion angles) are presented. It is noted that pseudotetrahedral coordination of ligand donor centers around M(II) is typical for Mn(II), Co(II), Cu(II), and Zn(II), whereas for Fe(II) and Ni(II) it is almost planar. Values of standard enthalpy ΔH 0f,298 and standard Gibbs energy ΔG 0f,298 are positive for nearly all the complexes studied.

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Authors and Affiliations

  1. Kazan National Research Technological University, Kazan Branch, Joint Supercomputer Center, Russian Academy of Sciences, ul. K. Marksa 68, Kazan, Tatarstan, 420015, Russia

    O. V. Mikhailov & D. V. Chachkov

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  1. O. V. Mikhailov
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  2. D. V. Chachkov
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Correspondence to O. V. Mikhailov.

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Original Russian Text © O.V. Mikhailov, D.V. Chachkov, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 6, pp. 992–1000.

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Mikhailov, O.V., Chachkov, D.V. Comparative stability of isomeric (565)macrotricyclic chelates of 3d-elements formed in the systems M(II)-thiosemicarbazide-formaldehyde according to DFT B3LYP data. Russ J Gen Chem 83, 1123–1130 (2013). https://doi.org/10.1134/S1070363213060200

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