Intramolecular Hydrogen Atom Transfer in Aminyl Radical at Room Temperature with Large Kinetic Isotope Effect,Journal of the American Chemical Society

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Intramolecular Hydrogen Atom Transfer in Aminyl Radical at Room Temperature with Large Kinetic Isotope Effect
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-05-17 00:00:00 , DOI: 10.1021/jacs.7b02692
Ying Wang ₁ , Arnon Olankitwanit ₁ , Suchada Rajca ₁ , Andrzej Rajca ₁

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We report a large kinetic isotope effect at 298 K, k_H/k_D ≈ 150, associated with an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) in the decay of a PEGylated carbazyl (aminyl) radical in solution. The experimental observations surprisingly combine the hallmarks of tunneling, including large KIEs and unusual activation parameters, with linear Arrhenius and Eyring plots over an exceptionally wide temperature range of 116 K.

中文翻译：

室温下氨自由基中分子内氢原子转移的动力学同位素效应

我们在298K报告一个大动力学同位素效应，ķ _ħ / ķ _d ≈150，与聚乙二醇化的咔唑基（aminyl）的衰减的分子内1,5-氢原子转移（1,5- HAT）在溶液中的自由基相关联。实验观察到的结果令人惊讶地将隧穿的标志（包括大的KIE和异常的激活参数）与116 K的超宽温度范围内的线性Arrhenius和Eyring图结合在一起。

更新日期：2017-05-23

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