Full Text Available
Note: Clicking the button above will open the full text document at the original institutional repository in a new window.
A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes†
An article published by Elsevier and also available at DOI: 10.1039/c3dt50539a
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2020
|
| Tags: |
No Tags, Be the first to tag this record!
|
| _version_ | 1867613137978523648 |
|---|---|
| access_status_str | Open Access |
| author | Aniagyei, Albert Tia, Richard Adei, Evans |
| author_browse | Adei, Evans Aniagyei, Albert Tia, Richard |
| author_facet | Aniagyei, Albert Tia, Richard Adei, Evans |
| author_sort | Aniagyei, Albert |
| collection | Thesis |
| description | An article published by Elsevier and also available at DOI: 10.1039/c3dt50539a |
| format | Article |
| id | oai:ir.knust.edu.gh:123456789/12672 |
| institution | KNUST (Ghana) |
| language | English |
| last_indexed | 2026-06-10T12:31:22.621Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from KNUSTSpace — Kwame Nkrumah University of Science & Technology (Ghana) |
| publishDate | 2020 |
| publishDateRange | 2020 |
| publishDateSort | 2020 |
| publisher | Elsevier |
| publisherStr | Elsevier |
| record_format | dspace |
| source_str | KNUSTSpace — Kwame Nkrumah University of Science & Technology (Ghana) |
| spelling | oai:ir.knust.edu.gh:123456789/12672 A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† Aniagyei, Albert Tia, Richard Adei, Evans An article published by Elsevier and also available at DOI: 10.1039/c3dt50539a The oxo complexes of group VII B are of great interest for their potential toward epoxidation and dihy-droxylation. In this work, the mechanisms of oxidation of ethylene by rhenium-oxo complexes of thetype LReO3(L = O−, Cl, CH3, OCH3, Cp, NPH3) have been explored at the B3LYP/LACVP* level of theory.The activation barriers and reaction energies for the stepwise and concerted addition pathways involvingmultiple spin states have been computed. In the reaction of LReO3(L = O−, Cl, CH3, OCH3, Cp, NPH3) withethylene, it was found that the concerted [3 + 2] addition pathway on the singlet potential energy sur-faces leading to the formation of a dioxylate intermediate is favored over the [2 + 2] addition pathwayleading to the formation of a metallaoxetane intermediate and its re-arrangement to form the dioxylate.The activation barrier for the formation of the dioxylate on the singlet PES for the ligands studied isfound to follow the order O−>CH3> NPH3>CH3O−>Cl−> Cp and the reaction energies follow theorder CH3>O−> NPH3>CH3O−>Cl−> Cp. On the doublet PES, the [2 + 2] addition leading to the for-mation the metallaoxetane intermediate is favored over dioxylate formation for the ligands L = CH3,CH3O−,Cl−. The activation barriers for the formation of the metallaoxetane intermediate are found toincrease for the ligands in the order CH3<Cl−<CH3O−while the reaction energies follow the order Cl−<CH3O−<CH3. The subsequent re-arrangement of the metallaoxetane intermediate to the dioxylate isonly feasible in the case of ReO3(OCH3). Of all the complexes studied, the best dioxylating catalyst isReO3Cp (singlet surface); the best epoxidation catalyst is ReO3Cl (singlet surface); and the best metalla-oxetane formation catalyst is ReO3(NPH3) (triplet surface). KNUST 2020-07-08T16:07:30Z 2023-04-19T02:09:06Z 2020-07-08T16:07:30Z 2023-04-19T02:09:06Z 2013-04-01 Article DaltonTrans., 2013,42, 10885 https://ir.knust.edu.gh/handle/123456789/12672 en application/pdf Elsevier |
| spellingShingle | Aniagyei, Albert Tia, Richard Adei, Evans A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title | A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title_full | A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title_fullStr | A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title_full_unstemmed | A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title_short | A density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| title_sort | density functional theory study of the mechanisms of oxidation of ethylene by rhenium oxide complexes† |
| url | https://ir.knust.edu.gh/handle/123456789/12672 |
| work_keys_str_mv | AT aniagyeialbert adensityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes AT tiarichard adensityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes AT adeievans adensityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes AT aniagyeialbert densityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes AT tiarichard densityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes AT adeievans densityfunctionaltheorystudyofthemechanismsofoxidationofethylenebyrheniumoxidecomplexes |