Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes
Transition-metal-mediated oxygen transfer reactions are of importance in both industry and academia; thus, a series of rhenium oxo complexes of the type ReO3L (L = O−, Cl−, F−, OH−, Br−, I−) and their effects as oxidation catalysts on ethylene have been studied. The activation and reaction energies...
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| Format: | Article |
| Language: | English |
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Wiley
2021-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2021/7931956 |
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| author | Emmanuel Adu Fosu Collins Obuah Louis Hamenu Albert Aniagyei Michael Kojo Ainooson Krishna K. Govender |
| author_facet | Emmanuel Adu Fosu Collins Obuah Louis Hamenu Albert Aniagyei Michael Kojo Ainooson Krishna K. Govender |
| author_sort | Emmanuel Adu Fosu |
| collection | DOAJ |
| description | Transition-metal-mediated oxygen transfer reactions are of importance in both industry and academia; thus, a series of rhenium oxo complexes of the type ReO3L (L = O−, Cl−, F−, OH−, Br−, I−) and their effects as oxidation catalysts on ethylene have been studied. The activation and reaction energies for the addition pathways involving multiple spin states (singlet and triplet) have been computed. In all cases, structures on the singlet potential energy surfaces showed higher stability compared to their counterparts on the triplet potential energy surfaces (PESs). Frontier Molecular Orbital calculations show electrons flow from the HOMO of ethylene to the LUMO of rhenium for all complexes studied except ReO4− where the reverse case occurs. In the reaction between ReO3L (L = O−, Cl−, F−, OH−, Br−, and I−) and ethylene, the concerted [3 + 2] addition pathway on the singlet PES leading to the formation of dioxylate intermediate is favored over the [2 + 2] addition pathway leading to the formation of a metallaoxetane intermediate and subsequent rearrangement to the dioxylate. The activation and the reaction energies for the formation of the dioxylate on the singlet PES for the ligands studied followed the order O− > OH− > I− > F− > Br− > Cl− and O− > OH− > F− > I− > Br− > Cl−, respectively. Furthermore, the activation and the reaction energies for the formation of the metallaoxetane intermediate increase in the order O− > OH− > I− > Br− > Cl− > F− and O− > Br− > I− > Cl− > OH− > F−, respectively. The subsequent rearrangement of the metallaoxetane intermediate to the dioxylate is only feasible in the case of ReO4−. Of all the complexes studied, the best dioxylating catalyst is ReO3Cl (singlet surface) and the best epoxidation catalyst is ReO3F (singlet surface). |
| format | Article |
| id | doaj-art-80d12a1d9a4e436b912373e9d6500ea9 |
| institution | Kabale University |
| issn | 2090-9063 2090-9071 |
| language | English |
| publishDate | 2021-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Chemistry |
| spelling | doaj-art-80d12a1d9a4e436b912373e9d6500ea92025-02-03T05:43:46ZengWileyJournal of Chemistry2090-90632090-90712021-01-01202110.1155/2021/79319567931956Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo ComplexesEmmanuel Adu Fosu0Collins Obuah1Louis Hamenu2Albert Aniagyei3Michael Kojo Ainooson4Krishna K. Govender5Department of Chemistry, University of Ghana, Legon, Accra, GhanaDepartment of Chemistry, University of Ghana, Legon, Accra, GhanaDepartment of Chemistry, University of Ghana, Legon, Accra, GhanaSchool of Basic and Biomedical Sciences, University of Health and Allied Sciences, Ho, GhanaDepartment of Chemistry, University of Ghana, Legon, Accra, GhanaDepartment of Chemical Sciences, University of Johannesburg, P. O. Box 17011, Doornfontein Campus, Johannesburg 2028, South AfricaTransition-metal-mediated oxygen transfer reactions are of importance in both industry and academia; thus, a series of rhenium oxo complexes of the type ReO3L (L = O−, Cl−, F−, OH−, Br−, I−) and their effects as oxidation catalysts on ethylene have been studied. The activation and reaction energies for the addition pathways involving multiple spin states (singlet and triplet) have been computed. In all cases, structures on the singlet potential energy surfaces showed higher stability compared to their counterparts on the triplet potential energy surfaces (PESs). Frontier Molecular Orbital calculations show electrons flow from the HOMO of ethylene to the LUMO of rhenium for all complexes studied except ReO4− where the reverse case occurs. In the reaction between ReO3L (L = O−, Cl−, F−, OH−, Br−, and I−) and ethylene, the concerted [3 + 2] addition pathway on the singlet PES leading to the formation of dioxylate intermediate is favored over the [2 + 2] addition pathway leading to the formation of a metallaoxetane intermediate and subsequent rearrangement to the dioxylate. The activation and the reaction energies for the formation of the dioxylate on the singlet PES for the ligands studied followed the order O− > OH− > I− > F− > Br− > Cl− and O− > OH− > F− > I− > Br− > Cl−, respectively. Furthermore, the activation and the reaction energies for the formation of the metallaoxetane intermediate increase in the order O− > OH− > I− > Br− > Cl− > F− and O− > Br− > I− > Cl− > OH− > F−, respectively. The subsequent rearrangement of the metallaoxetane intermediate to the dioxylate is only feasible in the case of ReO4−. Of all the complexes studied, the best dioxylating catalyst is ReO3Cl (singlet surface) and the best epoxidation catalyst is ReO3F (singlet surface).http://dx.doi.org/10.1155/2021/7931956 |
| spellingShingle | Emmanuel Adu Fosu Collins Obuah Louis Hamenu Albert Aniagyei Michael Kojo Ainooson Krishna K. Govender Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes Journal of Chemistry |
| title | Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes |
| title_full | Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes |
| title_fullStr | Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes |
| title_full_unstemmed | Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes |
| title_short | Quantum Mechanistic Studies of the Oxidation of Ethylene by Rhenium Oxo Complexes |
| title_sort | quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes |
| url | http://dx.doi.org/10.1155/2021/7931956 |
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