ELECTRON-PARAMAGNETIC RESONANCE-SPECTRA OF ALIPHATIC KETYL RADICAL-ANIONS IN FLUID SOLUTION
ELECTRON-PARAMAGNETIC RESONANCE-SPECTRA OF ALIPHATIC KETYL RADICAL-ANIONS IN FLUID SOLUTION
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DOI：
10.1039/p29920000163
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发表时间：
1992-02-01
期刊：
影响因子：
--
通讯作者：
NEVILLE, AG
中科院分区：
文献类型：
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作者：
DAVIES, AG;NEVILLE, AG
改进的方法已被开发用于在溶液中产生脂肪族酮基自由基阴离子，用于EPR光谱的研究。这些方法涉及钾在相应醇中的溶液的光解（其可能通过初始电子转移到溶剂中进行），或通过在强碱性条件下光解产生的叔丁氧基自由基从相应醇中提取氢原子。本文描述了一些新的醛、酮自由基离子的EPR谱，并与它们的共轭酸的EPR谱作了比较。发现丙酮自由基阴离子中的a（C-13-α）的值为52.2 G，证实其为非平面的。在环己酮自由基阴离子中环反转的Arrhenius参数为E（a）= 6.6 kcal mol-1，dagger和log（A/s-1）= 13.2。
Improved methods have been developed for generating aliphatic ketyl radical anions in solution for study by EPR spectroscopy. These methods involve either photolysis of a solution of potassium in the corresponding alcohol (which probably proceeds by initial electron transfer to the solvent), or abstraction of a hydrogen atom from the corresponding alcohol by photolytically generated tert-butoxyl radicals under strongly basic conditions. The EPR spectra of a number of new aldehyde and ketone radical ions are described, and compared with the spectra of their conjugate acids. The value of a(C-13-alpha) in the acetone radical anion is found to be 52.2 G confirming that it is non-planar. The Arrhenius parameters for the inversion of the ring in the cyclohexanone radical anion are E(a) = 6.6 kcal mol-1,dagger and log (A/s-1) = 13.2.