Photochemical generation and structure of vinyl radicals
Photochemical generation and structure of vinyl radicals
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DOI：
10.1002/ejoc.200700882
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发表时间：
2008-01-01
影响因子：
2.8
通讯作者：
Lodder, Gerrit
中科院分区：
文献类型：
--
作者：
Goumans, Theodorus P. M.;van Alem, Kai;Lodder, Gerrit
一系列E或Z立体异构体α-R取代的溴代苯乙烯(R=CH3，F或CN)在甲醇中光解生成E和/或Z立体异构体，它们来源于相应的乙烯基团。结果表明，α-Me乙烯基是一种快速平衡的弯曲结构，而α-F乙烯基是一种稳定的弯曲物种，与早期的热力学结果一致。根据立体化学结果，α-CN乙烯基被指定为快速反转键，而不是作为温度的函数的线性物种。乙醚中α-C(H)=O体系的立体化学数据表明，稳定的弯曲乙烯基是产物形成物种。这些结论得到了量子化学计算的支持。(C)Wiley-VCH Verlag GmbH&Co.KGaA，69451，德国温海姆，2008年)。
Photolysis of a series of E or Z stereoisomeric alpha-R-substituted bromostyrenes (R = CH3, F or CN) in methanol yields E and/or Z stereoisomeric styrenes, which stem from the corresponding vinyl radicals. The results show that the alpha-Me vinyl radical is a rapidly equilibrating, bent structure, while the alpha-F vinyl radical is a stable bent species, in agreement with earlier thermal results. The alpha-CN vinyl radical is assigned as a rapidly inverting bent and not a linear species from the stereochemical results as a function of temperature. Stereochemical data for the alpha-C(H)=O system in diethyl ether indicate a stable bent vinyl radical as product forming species. The conclusions are supported by quantum chemical computations. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).