Synthesis and Activity of Vanadium Oxo NHC Alkylidenes. Remarkable Preference for Degenerate Metathesis and Application for Carbon Isotope Exchange
V imido NHC phosphine alkylidenes are the most efficient V catalysts for ring-closing olefin metathesis of various terminal dienes. The presence of imido and phosphine ligands is responsible for catalyst decomposition. Therefore, the development of phosphine-free V oxo NHC alkylidenes is a logical n...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:280614 |
| Acceso en línea: | https://ddd.uab.cat/record/280614 https://dx.doi.org/urn:doi:10.1021/acs.organomet.2c00465 |
| Access Level: | acceso abierto |
| Sumario: | V imido NHC phosphine alkylidenes are the most efficient V catalysts for ring-closing olefin metathesis of various terminal dienes. The presence of imido and phosphine ligands is responsible for catalyst decomposition. Therefore, the development of phosphine-free V oxo NHC alkylidenes is a logical next step to further improve V-based olefin metathesis. Herein we report V oxo NHC chloride and alkoxide alkylidenes and their reactivity in olefin metathesis. V oxo NHC chloride is readily involved in cycloaddition/cycloreversion steps with olefins. However, a remarkable preference for the formation of a 1,3-metallacyclobutane (MCB) leads to exclusive methylene group exchange (degenerate metathesis) utilized for carbon isotope exchange. DFT studies further support the preference for the 1,3-MCB formation. |
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