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

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.