Synthesis and Unusual Reactivity of Acyl-Substituted 1,4-Disilacyclohexa-2,5-dienes

[Image: see text] 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(2)SiCl 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.