A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime
The C–X bond cleavage in different methyl halides (CH<sub>3</sub>X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (Co<sup>II</sup>Cbx) was theoretically investigated in the present work. An S<sub>N</sub>2-like mechanism was...
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| Format: | Article |
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MDPI AG
2022-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/21/7283 |
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| author | Luis E. Seijas Cesar H. Zambrano Vladimir Rodríguez Jorge Alí-Torres Luis Rincón F. Javier Torres |
| author_facet | Luis E. Seijas Cesar H. Zambrano Vladimir Rodríguez Jorge Alí-Torres Luis Rincón F. Javier Torres |
| author_sort | Luis E. Seijas |
| collection | DOAJ |
| description | The C–X bond cleavage in different methyl halides (CH<sub>3</sub>X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (Co<sup>II</sup>Cbx) was theoretically investigated in the present work. An S<sub>N</sub>2-like mechanism was considered to simulate the chemical process where the cobalt atom acts as the nucleophile and the halogen as the leaving group. The reaction path was computed by means of the intrinsic reaction coordinate method and analyzed in detail through the reaction force formalism, the quantum theory of atoms in molecules (QTAIM), and the calculation of one-electron density derived quantities, such as the source function (SF) and the spin density. A thorough comparison of the results with those obtained in the same reaction occurring in presence of 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(I) (Co<sup>I</sup>Cbx) was conducted to reveal the main differences between the two cases. The reactions mediated by Co<sup>II</sup>Cbx were observed to be endothermic and possess higher activation energies in contrast to the reactions where the Co<sup>I</sup>Cbx complex is present. The latter was supported by the reaction force results, which suggest a relationship between the activation energy and the ionization potentials of the different nucleophiles present in the cleavage reaction. Moreover, the SF results indicates that the lower axial ligand (i.e., 5,6-dimethylbenzimidazole) exclusively participates on the first stage of the reaction mediated by the Co<sup>II</sup>Cbx complex, while for the Co<sup>I</sup>Cbx case, it appears to have an important role along the whole process. Finally, the QTAIM charge analysis indicates that oxidation of the cobalt atom occurs in both cases; at the same time, it suggests the formation of an uncommon two-center one-electron bond in the Co<sup>II</sup>Cbx case. The latter was confirmed by means of electron localization calculations, which resulted in a larger electron count at the Co–C interatomic region for the Co<sup>I</sup>Cbx case upon comparison with its Co<sup>II</sup>Cbx counterpart. |
| first_indexed | 2024-03-09T18:48:48Z |
| format | Article |
| id | doaj.art-51dafdc8823b4761a131a2772f9e066e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T18:48:48Z |
| publishDate | 2022-10-01 |
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| series | Molecules |
| spelling | doaj.art-51dafdc8823b4761a131a2772f9e066e2023-11-24T06:01:34ZengMDPI AGMolecules1420-30492022-10-012721728310.3390/molecules27217283A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)AloximeLuis E. Seijas0Cesar H. Zambrano1Vladimir Rodríguez2Jorge Alí-Torres3Luis Rincón4F. Javier Torres5Grupo de Química Computacional y Teórica (QCT-UR), Facultad de Ciencias Naturales, Universidad del Rosario, Bogotá 111221, ColombiaGrupo de Química Computacional y Teórica (QCT-USFQ), Departamento de Ingeniería Química, Universidad San Francisco de Quito, Diego de Robles y Vía Interoceánica, Quito 17-1200-841, EcuadorDepartamento de Matemática, Universidad San Francisco de Quito, Diego de Robles y Vía Interoceánica, Quito 17-1200-841, EcuadorDepartamento de Química, Universidad Nacional de Colombia, Av. Cra. 30 #45-03, Bogotá 111321, ColombiaGrupo de Química Computacional y Teórica (QCT-USFQ), Departamento de Ingeniería Química, Universidad San Francisco de Quito, Diego de Robles y Vía Interoceánica, Quito 17-1200-841, EcuadorGrupo de Química Computacional y Teórica (QCT-UR), Facultad de Ciencias Naturales, Universidad del Rosario, Bogotá 111221, ColombiaThe C–X bond cleavage in different methyl halides (CH<sub>3</sub>X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (Co<sup>II</sup>Cbx) was theoretically investigated in the present work. An S<sub>N</sub>2-like mechanism was considered to simulate the chemical process where the cobalt atom acts as the nucleophile and the halogen as the leaving group. The reaction path was computed by means of the intrinsic reaction coordinate method and analyzed in detail through the reaction force formalism, the quantum theory of atoms in molecules (QTAIM), and the calculation of one-electron density derived quantities, such as the source function (SF) and the spin density. A thorough comparison of the results with those obtained in the same reaction occurring in presence of 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(I) (Co<sup>I</sup>Cbx) was conducted to reveal the main differences between the two cases. The reactions mediated by Co<sup>II</sup>Cbx were observed to be endothermic and possess higher activation energies in contrast to the reactions where the Co<sup>I</sup>Cbx complex is present. The latter was supported by the reaction force results, which suggest a relationship between the activation energy and the ionization potentials of the different nucleophiles present in the cleavage reaction. Moreover, the SF results indicates that the lower axial ligand (i.e., 5,6-dimethylbenzimidazole) exclusively participates on the first stage of the reaction mediated by the Co<sup>II</sup>Cbx complex, while for the Co<sup>I</sup>Cbx case, it appears to have an important role along the whole process. Finally, the QTAIM charge analysis indicates that oxidation of the cobalt atom occurs in both cases; at the same time, it suggests the formation of an uncommon two-center one-electron bond in the Co<sup>II</sup>Cbx case. The latter was confirmed by means of electron localization calculations, which resulted in a larger electron count at the Co–C interatomic region for the Co<sup>I</sup>Cbx case upon comparison with its Co<sup>II</sup>Cbx counterpart.https://www.mdpi.com/1420-3049/27/21/7283reaction forceatoms in moleculessource functioncobaloximecarbon–halogen cleavage |
| spellingShingle | Luis E. Seijas Cesar H. Zambrano Vladimir Rodríguez Jorge Alí-Torres Luis Rincón F. Javier Torres A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime Molecules reaction force atoms in molecules source function cobaloxime carbon–halogen cleavage |
| title | A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime |
| title_full | A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime |
| title_fullStr | A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime |
| title_full_unstemmed | A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime |
| title_short | A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime |
| title_sort | theoretical study of the c x bond cleavage mediated by cob ii aloxime |
| topic | reaction force atoms in molecules source function cobaloxime carbon–halogen cleavage |
| url | https://www.mdpi.com/1420-3049/27/21/7283 |
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