The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study
Cationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts....
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2018-11-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.14.266 |
| _version_ | 1818620356190011392 |
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| author | Magdalena Jawiczuk Angelika Janaszkiewicz Bartosz Trzaskowski |
| author_facet | Magdalena Jawiczuk Angelika Janaszkiewicz Bartosz Trzaskowski |
| author_sort | Magdalena Jawiczuk |
| collection | DOAJ |
| description | Cationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts. In this work we performed computational studies on three cationic carbenes with the formal positive charge located at different distances from the carbene carbon. We show that the predicted initiation rates of Grubbs, indenylidene, and Hoveyda–Grubbs-like complexes incorporating these carbenes show little variance and are similar to initiation rates of standard Grubbs, indenylidene, and Hoveyda–Grubbs catalysts. In all investigated cases the partial charge of the carbene carbon atom is similar, resulting in comparable Ccarbene–Ru bond strengths and Ru–P/O dissociation Gibbs free energies. |
| first_indexed | 2024-12-16T17:52:04Z |
| format | Article |
| id | doaj.art-69df4e6fdecf4ea49c248f742df8b1ac |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-16T17:52:04Z |
| publishDate | 2018-11-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-69df4e6fdecf4ea49c248f742df8b1ac2022-12-21T22:22:16ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972018-11-011412872288010.3762/bjoc.14.2661860-5397-14-266The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT studyMagdalena Jawiczuk0Angelika Janaszkiewicz1Bartosz Trzaskowski2Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warszawa, PolandCentre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warszawa, PolandCentre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warszawa, PolandCationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts. In this work we performed computational studies on three cationic carbenes with the formal positive charge located at different distances from the carbene carbon. We show that the predicted initiation rates of Grubbs, indenylidene, and Hoveyda–Grubbs-like complexes incorporating these carbenes show little variance and are similar to initiation rates of standard Grubbs, indenylidene, and Hoveyda–Grubbs catalysts. In all investigated cases the partial charge of the carbene carbon atom is similar, resulting in comparable Ccarbene–Ru bond strengths and Ru–P/O dissociation Gibbs free energies.https://doi.org/10.3762/bjoc.14.266catalystscationic carbenesDFTinitiationmetathesis |
| spellingShingle | Magdalena Jawiczuk Angelika Janaszkiewicz Bartosz Trzaskowski The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study Beilstein Journal of Organic Chemistry catalysts cationic carbenes DFT initiation metathesis |
| title | The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study |
| title_full | The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study |
| title_fullStr | The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study |
| title_full_unstemmed | The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study |
| title_short | The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study |
| title_sort | influence of the cationic carbenes on the initiation kinetics of ruthenium based metathesis catalysts a dft study |
| topic | catalysts cationic carbenes DFT initiation metathesis |
| url | https://doi.org/10.3762/bjoc.14.266 |
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