An ab initio and density functional theory study of radical-clock reactions.
An ab initio and density functional theory study of radical-clock reactions.
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自由基时钟反应的从头算和密度泛函理论研究
DOI：
10.1021/jo702421m
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
T. Clark
中科院分区：
文献类型：
--
作者：
C. M. Jaeger;M. Hennemann;A. Mieszala;T. Clark
用密度泛函理论（DFT）和从头算（CBS-RAD）方法研究了一系列“自由基钟”反应。计算的活化能表明，这些自由基重排的障碍几乎完全由焓效应没有证据表明显着的极性效应。环戊基甲基自由基衍生物的闭环反应和环丙基甲基自由基的开环反应给出了计算的反应热和势垒之间的不同的相关性，但这两种类型的反应是内在一致的。
Density functional theory (DFT) and ab initio (CBS-RAD) calculations have been used to investigate a series of “radical clock” reactions. The calculated activation energies suggest that the barriers for these radical rearrangements are determined almost exclusively by the enthalpy effect with no evidence of significant polar effects. The ring-closure reactions to cyclopentylmethyl radical derivatives and the ring opening of cyclopropylmethyl radicals give different correlations between the calculated heat of reaction and barrier, but the two types of reaction are internally consistent.