Intramolecular Hydrogen Atom Transfer in Aminyl Radical at Room Temperature with Large Kinetic Isotope Effect

被引：18

作者：

Wang, Ying ^{[1
]}

Olankitwanit, Arnon ^{[1
]}

Rajca, Suchada ^{[1
]}

Rajca, Andrzej ^{[1
]}

机构：

[1] Univ Nebraska, Dept Chem, Lincoln, NE 68588 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 21期

关键词：

ORGANIC SPIN CLUSTERS; MACROCYCLIC POLYARYLMETHYL POLYRADICALS; PARAMAGNETIC-RESONANCE SPECTROSCOPY; C-H OXIDATION; 1,5-HYDROGEN SHIFT; ISOMERIZATION; DECOMPOSITION; COMPLEXES; BARRIER;

D O I：

10.1021/jacs.7b02692

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report a large kinetic isotope effect at 298 K, k(H)/k(D) approximate to 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.

引用

页码：7144 / 7147

页数：4

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