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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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-01, Vol.62 (4), p.e202215394-n/a
Main Authors: Nougué, Raphaël, Takahashi, Shintaro, Baceiredo, Antoine, Saffon‐Merceron, Nathalie, Branchadell, Vicenç, Kato, Tsuyoshi
Format: Article
Language:English
Subjects:
Cations
Chemical Sciences
Isomerization
Phosphine
Phosphines
Room temperature
Silylenes
Silylium Ions
Small Rings
Transition Metal Complexes
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Summary: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.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202215394