Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydrid...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:280631 |
| Acceso en línea: | https://ddd.uab.cat/record/280631 https://dx.doi.org/urn:doi:10.1021/acs.organomet.1c00425 |
| Access Level: | acceso abierto |
| Sumario: | V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydride elimination from unsubstituted metallacyclobutene is the primary decomposition pathway in those systems. Herein, we report the synthesis of the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)2Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that β-hydride elimination is significantly disfavored for V oxo species. |
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