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Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes

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dc.contributor.author Fosu, EA
dc.contributor.author Obuah, C
dc.contributor.author Hamenu, L
dc.contributor.author Aniagyei, A
dc.contributor.author Ainooson, MK
dc.contributor.author Govender, Krishna K
dc.date.accessioned 2021-09-22T08:22:11Z
dc.date.available 2021-09-22T08:22:11Z
dc.date.issued 2021-08
dc.identifier.citation Fosu, E., Obuah, C., Hamenu, L., Aniagyei, A., Ainooson, M. & Govender, K.K. 2021. Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes. <i>Journal of Chemistry, 2021.</i> http://hdl.handle.net/10204/12107 en_ZA
dc.identifier.issn 2090-9063
dc.identifier.issn 2090-9071
dc.identifier.uri https://doi.org/10.1155/2021/7931956
dc.identifier.uri http://hdl.handle.net/10204/12107
dc.description.abstract 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). en_US
dc.format Fulltext en_US
dc.language.iso en en_US
dc.relation.uri https://www.hindawi.com/journals/jchem/2021/7931956/ en_US
dc.source Journal of Chemistry, 2021 en_US
dc.subject Quantum mechanistic studies en_US
dc.subject Ethylene oxidation en_US
dc.subject Rhenium oxo complexes en_US
dc.title Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes en_US
dc.type Article en_US
dc.description.pages 11 en_US
dc.description.note Copyright © 2021 Emmanuel Adu Fosu et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. en_US
dc.description.cluster National Integrated Cyber InfraStructure en_US
dc.description.impactarea CHPC en_US
dc.identifier.apacitation Fosu, E., Obuah, C., Hamenu, L., Aniagyei, A., Ainooson, M., & Govender, K. K. (2021). Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes. <i>Journal of Chemistry, 2021</i>, http://hdl.handle.net/10204/12107 en_ZA
dc.identifier.chicagocitation Fosu, EA, C Obuah, L Hamenu, A Aniagyei, MK Ainooson, and Krishna K Govender "Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes." <i>Journal of Chemistry, 2021</i> (2021) http://hdl.handle.net/10204/12107 en_ZA
dc.identifier.vancouvercitation Fosu E, Obuah C, Hamenu L, Aniagyei A, Ainooson M, Govender KK. Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes. Journal of Chemistry, 2021. 2021; http://hdl.handle.net/10204/12107. en_ZA
dc.identifier.ris TY - Article AU - Fosu, EA AU - Obuah, C AU - Hamenu, L AU - Aniagyei, A AU - Ainooson, MK AU - Govender, Krishna K AB - 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). DA - 2021-08 DB - ResearchSpace DP - CSIR J1 - Journal of Chemistry, 2021 KW - Quantum mechanistic studies KW - Ethylene oxidation KW - Rhenium oxo complexes LK - https://researchspace.csir.co.za PY - 2021 SM - 2090-9063 SM - 2090-9071 T1 - Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes TI - Quantum mechanistic studies of the oxidation of ethylene by rhenium oxo complexes UR - http://hdl.handle.net/10204/12107 ER - en_ZA
dc.identifier.worklist 24924 en_US


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