Reversible Isomerization Between Silacyclopropyl Cation and Cyclic (Alkyl)(Amino)Silylene

A phosphine-stabilized silacyclopropyl cation 2 has been synthesized and fully characterized. Of particular interest, 2 reversibly isomerizes into the corresponding seven-membered cyclic (alkyl)(amino)silylene 3 at room temperature via a formal migratory ethylene insertion into the Si-P bond. Althou...

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Detalles Bibliográficos
Autores: Nougué, Raphaël, Takahashi, Shintaro, Baceiredo, Antoine, Saffon-Merceron, Nathalie, Branchadell, Vicenç|||0000-0003-3480-1669, Kato, Tsuyoshi|||0000-0001-9003-4455
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:285770
Acceso en línea:https://ddd.uab.cat/record/285770
https://dx.doi.org/urn:doi:10.1002/anie.202215394
Access Level:acceso abierto
Palabra clave:Isomerization
Silylenes
Silylium Ions
Small Rings
Transition Metal Complexes
Descripción
Sumario:A phosphine-stabilized silacyclopropyl cation 2 has been synthesized and fully characterized. Of particular interest, 2 reversibly isomerizes into the corresponding seven-membered cyclic (alkyl)(amino)silylene 3 at room temperature via a formal migratory ethylene insertion into the Si-P bond. Although silylene 3 has not been spectroscopically detected, its transient formation has been evidenced by the isolation of the corresponding disilene dimer 5 as well as by trapping reactions. A phosphine-stabilized silacyclopropyl cation has been synthesized and fully characterized. Interestingly, this silacyclopropyl cation reversibly isomerizes into the corresponding seven-membered cyclic (alkyl)(amino)silylene at room temperature via a formal migratory ethylene insertion into the Si-P bond. Although the silylene has not been spectroscopically detected, its transient formation has been evidenced by various trapping reactions.