화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.139, No.24, 8134-8137, 2017
From Si(II) to Si(IV) and Back: Reversible Intramolecular Carbon-Carbon Bond Activation by an Acyclic Iminosilylene
Reversibility is fundamental for transition metal catalysis, but equally for main group chemistry and especially low-valent silicon compounds, the interplay between oxidative addition and reductive elimination is key for a potential catalytic cycle. Herein, we report a highly reactive acyclic iminosilylsilylene 1, which readily performs an intramolecular insertion into a C=C bond of its aromatic ligand framework to give silacycloheptatriene (silepin) 2. UV-vis studies of this, Si(IV) compound indicated a facile transformation back to Si(II) at elevated temperatures, further supported by density functional theory calculations and experimentally demonstrated by isolation of a silylene-borane adduct 3 following addition of B(C6F3)(3). This tendency to undergo reductive elimination, was exploited in the investigation of silepin 2 as a synthetic equivalent of silylene in the activation of small molecules. In fact, the first monomeric, four coordinate silicon carbonate complex 4 was isolated and fully characterized in the reaction with carbon dioxide under mild conditions. Additionally, the exposure of 2 to 1 ethylene or molecular hydrogen gave silirane 5 and Si(IV) dihydride 6, respectively.