DMAP-stabilized bis(silyl)silylenes as versatile synthons for organosilicon compounds

Abstract

DMAP-stabilized silylenes 1a–c are obtained from the reductive debromination of the corresponding dibromosilanes in the presence of DMAP. Their distinctly different thermal isomerization reactions via C–H bond activation, dearomative ring expansion and silyl migration are discussed. Furthermore, complexes 1 dissociate at elevated temperatures, providing the corresponding free silylenes in situ, which are even capable of single-site activation of H₂. Additionally, a potassium-substituted silicon-centered radical 2 is isolated from overreduction of (^tBu₃Si)₂SiBr₂.