School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 102488, P. R. China.
Institute of Inorganic Chemistry, Georg-August-Universität Göttingen, Tammannstrasse 4, 37077, Göttingen, Germany.
Chemistry. 2019 Jan 24;25(5):1193-1197. doi: 10.1002/chem.201805267. Epub 2018 Dec 14.
Lewis base cAACs stabilized monomeric silylenes with halogen or methyl substituents at the silicon center have not been reported due to the strong σ-donor and π-acceptor character of cAAC. To prepare these monomeric silylenes, we used the silicon(IV) precursors 5 and 6 with a nitrogen donor group L (L=o-C H NMe ). The cAAC-stabilized (cAAC=C(CH )(CMe ) N-Ar, Ar=2,6-iPr C H ) silylenes LSiCl(cAAC) (7) and LSiMe(cAAC) (8) were synthesized by reduction of LSiCl and LSiMeCl with two equivalents of KC in the presence of one equivalent of cAAC, respectively. Compounds 7 and 8 were characterized by single-crystal X-ray crystallography, NMR spectroscopy, and elemental analysis. Compounds 7 and 8 are stable in the solid state as well as in solution at room temperature for at least four months under inert conditions.
由于 cAAC 的强 σ-给体和 π-受体性质，Lewis 碱 cAAC 稳定的具有卤素或甲基取代基的硅中心的单体硅烯尚未有报道。为了制备这些单体硅烯，我们使用了带有氮供体基团 L（L=o-C H NMe ）的硅（IV）前体 5 和 6。通过在 KC 的存在下，分别用两倍当量的 LSiCl 和 LSiMeCl 还原 LSiCl(cAAC)（7）和 LSiMe(cAAC)（8）。通过单晶 X 射线晶体学、NMR 光谱和元素分析对化合物 7 和 8 进行了表征。在惰性条件下，化合物 7 和 8 在固态以及在室温下的溶液中至少稳定四个月。
