DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands
Based on the results of a quantum chemical calculation using the DFT method with the OPBE/TZVP and B3PW91/TZVP levels, the possibility of the existence of three cobalt heteroligand complexes containing in the inner coordination sphere porphyrazine, di[benzo]- and tetra[benzo]porphyrazine, and two ox...
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| Format: | Article |
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MDPI AG
2020-11-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/21/23/9085 |
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| author | Oleg V. Mikhailov Denis V. Chachkov |
| author_facet | Oleg V. Mikhailov Denis V. Chachkov |
| author_sort | Oleg V. Mikhailov |
| collection | DOAJ |
| description | Based on the results of a quantum chemical calculation using the DFT method with the OPBE/TZVP and B3PW91/TZVP levels, the possibility of the existence of three cobalt heteroligand complexes containing in the inner coordination sphere porphyrazine, di[benzo]- and tetra[benzo]porphyrazine, and two oxygen (O<sup>2−</sup>) ions with probable oxidation state VI of Co, which is unknown for this element at the present time, was shown. Data on the structural parameters are presented. It was shown that CoN<sub>4</sub> chelate nodes as well as all metal-chelate and non-chelate cycles in each of these complexes, were strictly planar. Besides, the bond angles formed by two donor nitrogen atoms and a Co atom were close or equal to 90°, while the bond angles formed by donor atoms N, Co, and O, in most cases, albeit insignificantly, differed from this value. Good agreement between the calculated data obtained using the above two versions of the DFT method was found. Standard thermodynamic parameters of formation (standard enthalpy Δ<i>H</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub>, entropy <i>S</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub> and Gibbs’s energy Δ<i>G</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub>) for the indicated complexes were presented too. |
| first_indexed | 2024-03-10T14:28:09Z |
| format | Article |
| id | doaj.art-5f83f48bb4e64cbeb43b9d649b04d00b |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T14:28:09Z |
| publishDate | 2020-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-5f83f48bb4e64cbeb43b9d649b04d00b2023-11-20T22:50:35ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672020-11-012123908510.3390/ijms21239085DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido LigandsOleg V. Mikhailov0Denis V. Chachkov1Kazan National Research Technological University, K. Marx Street 68, 420015 Kazan, RussiaKazan Department of Joint Supercomputer Center of Russian Academy of Sciences—Branch of Federal Scientific Center “Scientific Research Institute for System Analysis of the RAS”, Lobachevskii Street 2/31, 420111 Kazan, RussiaBased on the results of a quantum chemical calculation using the DFT method with the OPBE/TZVP and B3PW91/TZVP levels, the possibility of the existence of three cobalt heteroligand complexes containing in the inner coordination sphere porphyrazine, di[benzo]- and tetra[benzo]porphyrazine, and two oxygen (O<sup>2−</sup>) ions with probable oxidation state VI of Co, which is unknown for this element at the present time, was shown. Data on the structural parameters are presented. It was shown that CoN<sub>4</sub> chelate nodes as well as all metal-chelate and non-chelate cycles in each of these complexes, were strictly planar. Besides, the bond angles formed by two donor nitrogen atoms and a Co atom were close or equal to 90°, while the bond angles formed by donor atoms N, Co, and O, in most cases, albeit insignificantly, differed from this value. Good agreement between the calculated data obtained using the above two versions of the DFT method was found. Standard thermodynamic parameters of formation (standard enthalpy Δ<i>H</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub>, entropy <i>S</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub> and Gibbs’s energy Δ<i>G</i><sup>0</sup><i><sub>f</sub></i><sub>, 298</sub>) for the indicated complexes were presented too.https://www.mdpi.com/1422-0067/21/23/9085oxidation state VIcobaltmacrocyclic chelateoxo ligandporphyrazinebenzo-derivative |
| spellingShingle | Oleg V. Mikhailov Denis V. Chachkov DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands International Journal of Molecular Sciences oxidation state VI cobalt macrocyclic chelate oxo ligand porphyrazine benzo-derivative |
| title | DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands |
| title_full | DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands |
| title_fullStr | DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands |
| title_full_unstemmed | DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands |
| title_short | DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands |
| title_sort | dft quantum chemical modeling molecular structures of cobalt macrocyclic complexes with porphyrazine or its benzo derivatives and two oxygen acido ligands |
| topic | oxidation state VI cobalt macrocyclic chelate oxo ligand porphyrazine benzo-derivative |
| url | https://www.mdpi.com/1422-0067/21/23/9085 |
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