Computational prediction on the catalytic activity of heterobimetallic complex featuring MM' triple bond in acetylene cyclotrimerization : Mechanistic study
© 2020 Wiley Periodicals LLC.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 42(2021), 7 vom: 15. März, Seite 484-491 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2021
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article acetylene cyclotrimerization catalyst design heterobimetallic complexes reaction mechanism |
| Zusammenfassung: | © 2020 Wiley Periodicals LLC. A detailed reaction mechanism of acetylene cyclotrimerization catalyzed by V(i PrNPMe2 )3 Fe-PMe3 (denote as CAT), a heterobimetallic complex featuring V-Fe triple bond, was computationally investigated using density functional theory. The calculated results show that the first acetylene firstly attaches to the V atom of CAT to get a four-membered ring structure through [2 + 2] cycloaddition reaction. For the second acetylene addition, there are two cyclotrimerization mechanisms, outer sphere mechanism and inner mechanism. The inner sphere reaction pathway is the main reaction pathway. By replacing the V with Nb and Ta, Fe with Ru and Os, a series of new catalysts are screened computationally. The calculated results show that, all of the nine heterobimetallic complexes show high activity at mild condition. The energy barrier of the rate determining step is related to the natural population analysis (NPA) charge of M' and the Wiberg bond index (WBI) of M-M' bond. The more negative NPA charge of M' and the smaller WBI of M-M' bond, the lower energy barrier is |
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| Beschreibung: | Date Revised 29.01.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.26471 |