Abstract
In continuation of our recent studies on group 14 rings with exocyclic silicon-carbon double bonds, we report here on the synthesis and reactivity of previously unknown acyl-substituted 1,4-disilacyclohexa-2,5-dienes. 1,1,4,4-Tetrakistrimethylsilyl-1,4-disilacyclohexa-2,5-diene 1 cleanly afforded the silyl anion 1-K after addition of 1 equiv of KO t Bu. 1-K subsequently could be reacted with various electrophiles to the expected substitution products including compounds 4 and 5. When photolyzed with λ > 300 nm radiation, 4 and 5 undergo Brook-type 1,3-Si → O migration reactions to generate the corresponding 1,4-disilacyclohexadienes with exocyclic Si=C bonds as the primary products. These metastable silenes only could be characterized in form of appropriate quenching products. The reaction of compound 4 with KO t Bu followed by the addition of 1 equiv of PhMe 2SiCl surprisingly gave the silylated 1,4-disilanorbornadiene cages 8 and 9 instead of the expected exocyclic silene. The responsible sila-Peterson-type mechanism could be elucidated by density functional theory calculations at the conductor-like polarizable continuum model (THF) B3LYP-GD3/6-31 + G(d) level and by the isolation and characterization of unstable intermediate products after proper derivatization.
Originalsprache | englisch |
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Seiten (von - bis) | 3686-3696 |
Seitenumfang | 11 |
Fachzeitschrift | Organometallics |
Jahrgang | 41 |
Ausgabenummer | 23 |
DOIs | |
Publikationsstatus | Veröffentlicht - 12 Dez. 2022 |
ASJC Scopus subject areas
- Anorganische Chemie
- Physikalische und Theoretische Chemie
- Organische Chemie