Organic Chemistry Institute, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland.
J Am Chem Soc. 2011 Aug 10;133(31):11844-6. doi: 10.1021/ja2040392. Epub 2011 Jul 18.
In 2,6-diarylphenylSiR(2) cations, the 2,6-diarylphenyl (m-terphenyl) scaffold blocks incoming nucleophiles and stabilizes the positive charge at silicon by lateral ring interactions. Direct ortho-halogen and π-electron-rich face coordination to silicon has been seen. For a series of cations bearing 2,6-difluoro-2',6'-dimethyl-X(n)-substituted rings, the relative contribution of these two modes of stabilization has been assessed. Direct coordination from an aryl fluoride is found to be comparable to that from the mesityl π-face.
在 2,6-二芳基硅基阳离子中，2,6-二芳基（间三联苯）骨架通过侧环相互作用阻止亲核试剂的进攻并稳定硅上的正电荷。人们已经观察到直接邻位卤化和π-富电子面配位到硅上。对于一系列带有 2,6-二氟-2',6'-二甲基-X(n)-取代环的阳离子，评估了这两种稳定模式的相对贡献。发现芳基氟化物的直接配位与mesityl π-面的配位相当。
