通过氧化还原切换控制锥体反转速率。
Control of pyramidal inversion rates by redox switching.
作者信息
Davies Mark W, Shipman Michael, Tucker James H R, Walsh Tiffany R
机构信息
Department of Chemistry, University of Warwick, Coventry, UK.
出版信息
J Am Chem Soc. 2006 Nov 8;128(44):14260-1. doi: 10.1021/ja065325f.
PMID:17076491
Abstract
The dynamics of pyramidal nitrogen inversion can be controlled by reversible redox switching in trans-2,3-diphenylaziridines bearing a suitable 1,4-naphthaquinone substituent. In the reduced form, an intramolecular H-bond significantly raises the inversion barrier slowing this molecular motion by >50-fold. The experimental findings are further supported by DFT calculations.
摘要
在带有合适的1,4-萘醌取代基的反式-2,3-二苯基氮杂环丙烷中，金字塔形氮翻转的动力学可以通过可逆的氧化还原切换来控制。在还原形式下，分子内氢键显著提高了翻转势垒，使这种分子运动减慢了50倍以上。密度泛函理论计算进一步支持了实验结果。
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