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Dostęp zamkniętyOlefin Metathesis Catalyzed by a Hoveyda–Grubbs-like Complex Chelated to Bis(2-mercaptoimidazolyl) Methane: A Predictive DFT Study
| dc.abstract.en | Although highly selective complexes for the cross-metathesis of olefins, particularly oriented toward the productive metathesis of Z-olefins, have been reported in recent years, there is a constant need to design and prepare new and improved catalysts for this challenging reaction. In this work, guided by density functional theory (DFT) calculations, the performance of a Ru-based catalyst chelated to a sulfurated pincer in the olefin metathesis was computationally assessed. The catalyst was designed based on the Hoveyda–Grubbs catalyst (SIMes)Cl2Ru(═CH–o–OiPrC6H4) through the substitution of chlorides with the chelator bis(2-mercaptoimidazolyl)methane. The obtained thermodynamic and kinetic data of the initiation phase through side- and bottom-bound mechanisms suggest that this system is a versatile catalyst for olefin metathesis, as DFT predicts the highest energy barrier of the catalytic cycle of ca. 20 kcal/mol, which is comparable to those corresponding to the Hoveyda–Grubbs-type catalysts. Moreover, in terms of the stereoselectivity evaluated through the propagation phase in the metathesis of propene–propene to 2-butene, our study reveals that the Z isomer can be formed under a kinetic control. We believe that this is an interesting outcome in the context of future exploration of Ru-based catalysts with sulfurated chelates in the search for high stereoselectivity in selected reactions. |
| dc.affiliation | Uniwersytet Warszawski |
| dc.contributor.author | Trzaskowski, Bartosz |
| dc.contributor.author | Martínez, J. Pablo |
| dc.date.accessioned | 2024-01-25T15:43:53Z |
| dc.date.available | 2024-01-25T15:43:53Z |
| dc.date.issued | 2022 |
| dc.description.finance | Publikacja bezkosztowa |
| dc.description.number | 5 |
| dc.description.volume | 126 |
| dc.identifier.doi | 10.1021/ACS.JPCA.1C09336 |
| dc.identifier.issn | 1089-5639 |
| dc.identifier.uri | https://repozytorium.uw.edu.pl//handle/item/114586 |
| dc.identifier.weblink | https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.1c09336 |
| dc.language | eng |
| dc.pbn.affiliation | chemical sciences |
| dc.relation.ispartof | Journal of Physical Chemistry A |
| dc.relation.pages | 720-732 |
| dc.rights | ClosedAccess |
| dc.sciencecloud | nosend |
| dc.title | Olefin Metathesis Catalyzed by a Hoveyda–Grubbs-like Complex Chelated to Bis(2-mercaptoimidazolyl) Methane: A Predictive DFT Study |
| dc.type | JournalArticle |
| dspace.entity.type | Publication |