为什么[PhSiO(1.5)](8,10,12)笼主要在邻位发生自溴化反应？模型研究表明笼对该反应机理有强烈影响。
Why do the [PhSiO(1.5)](8,10,12) cages self-brominate primarily in the ortho position? Modeling reveals a strong cage influence on the mechanism.
作者信息
Bahrami M, Hashemi H, Ma X, Kieffer J, Laine R M
机构信息
Dept. of Mater. Sci. & Eng, Univ. of Michigan, Ann Arbor, MI 48109, USA.
出版信息
Phys Chem Chem Phys. 2014 Dec 21;16(47):25760-4. doi: 10.1039/c4cp03997a. Epub 2014 Oct 30.
PMID:25354544
Abstract
(PhSiO1.5)8,10,12 cages are bulky, electron withdrawing like CF3; yet self-brominate (60 °C), favoring ortho substitution: PhT8 (≈85%), PhT10 (≈75%) and PhT12 (60%). First-principles calculations suggest bromination initiates when Br2 is "trapped" via H-bonding to ortho-H's, followed by polarization via strong interactions with cage faces, possibly cage LUMOs.
摘要
（PhSiO1.5）8、10、12笼体积庞大，像CF3一样具有吸电子性；但能进行自溴化反应（60℃），有利于邻位取代：PhT8（约85%）、PhT10（约75%）和PhT12（60%）。第一性原理计算表明，当Br2通过与邻位氢形成氢键而“被俘获”时，溴化反应开始，随后通过与笼面（可能是笼的最低未占分子轨道）的强相互作用发生极化。
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