A new type of N-heterocyclic silylene with ambivalent reactivity.
The synthesis of a novel divalent silicon compound by debromination of the corresponding dibromosilyl precursor is reported. The silylene possesses a unique reactivity toward electrophiles of the type R-X (R = H, silyl; X = halogen, triflate) in comparison with the germanium congener. DFT calculations suggest that this is due to a much higher basicity of the silylene versus that of germylene lone-pair electrons. Thus, addition of Me3SiX to the silylene (X = OSO2CF3, triflate) furnishes the corresponding (kinetically favored) 1,4-adduct which subsequently rearranges to the thermodynamically favored 1,1-adduct.
Driess
Matthias
M
Institute of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, D-10623 Berlin, Germany. matthias.driess@tu-berlin.de
Yao
Shenglai
S
Brym
Markus
M
van Wüllen
Christoph
C
Lentz
Dieter
D