Structure and reactivity of radical ions: new twists on old concepts.
Structure and reactivity of radical ions: new twists on old concepts.
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DOI：
10.1002/chem.200600554
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发表时间：
2006-09-18
期刊：
影响因子：
--
通讯作者：
Wiest, Olaf
中科院分区：
文献类型：
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作者：
Donoghue, Patrick J;Wiest, Olaf
电子转移是最简单的反应，但它对有机化合物的结构和反应性有着深远的影响。这些变化使人们对一些用于解释有机化学的基本概念有了新的认识，比如对称、芳香性和键合。利用高阶电子结构计算的结果分析了简单碳氢化合物与自由基阳离子的周环反应的机理差异。讨论了态对称相关、Jahn-Teller扭曲、离域和分数键对烃基阳离子反应途径的重要性。
Electron transfer is the simplest reaction possible, yet it has a profound impact on the structure and reactivity of organic compounds. These changes allow a new look at some of the fundamental concepts that are used to explain organic chemistry, such as symmetry, aromaticity, and bonding. The results from high-level electronic structure calculations are used to analyze the mechanistic differences in the pericyclic reactions of simple hydrocarbons and their radical cation counterparts. The importance of state symmetry correlation, Jahn-Teller distortions, delocalization, and fractional bonding for the reaction pathways of hydrocarbon radical cations is discussed.