Reversible Isomerization Between Silacyclopropyl Cation and Cyclic (Alkyl)(Amino)Silylene
Nougué, Raphaël (Université de Toulouse)
Takahashi, Shintaro (Université de Toulouse)
Baceiredo, Antoine (Université de Toulouse)
Saffon-Merceron, Nathalie (Université de Toulouse)
Branchadell Gallo, Vicenç (Universitat Autònoma de Barcelona. Departament de Química)
Kato, Tsuyoshi (Université de Toulouse)

Data:	2022
Resum:	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.
Ajuts:	European Commission 306658 Agencia Estatal de Investigación PID2020-116861GB-I00
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Matèria:	Isomerization ; Silylenes ; Silylium Ions ; Small Rings ; Transition Metal Complexes
Publicat a:	Angewandte Chemie (International ed. Internet), Vol. 62, Num. 4 (December 2022) , art. e202215394, ISSN 1521-3773

DOI: 10.1002/anie.202215394
PMID: 36445806

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