TY - JOUR
T1 - Synthesis and Unusual Reactivity of Acyl-Substituted 1,4-Disilacyclohexa-2,5-dienes
AU - Schuh, Lukas
AU - Torvisco, Ana
AU - Flock, Michaela
AU - Grogger, Christa
AU - Stueger, Harald
N1 - © 2022 The Authors. Published by American Chemical Society.
PY - 2022/12/12
Y1 - 2022/12/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85141955734&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.2c00475
DO - 10.1021/acs.organomet.2c00475
M3 - Article
C2 - 36533114
SN - 0276-7333
VL - 41
SP - 3686
EP - 3696
JO - Organometallics
JF - Organometallics
IS - 23
ER -