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	Theoretical studies of the effects of substituents on the ring opening reactions for the cyclopropylcarbinyl radical
	Zhang, Qing-Li; Chen, Bo-Zhen
刊名	Journal of molecular structure-theochem
	2010-02-15
卷号	941期号:1-3页码:10-21
关键词	Density functional theory The cyclopropylcarbinyl radical Radical reactions Reaction rate constants
ISSN号	0166-1280
DOI	10.1016/j.theochem.2009.10.029
通讯作者	Chen, bo-zhen(bozhenchen@hotmail.com)
英文摘要	Dft (u)b3lyp/6-31g(d,p), (u)b3lyp/6-31+g(d,p), and (u)b3lyp/6-311+g(d,p) calculations were carried out to investigate the ring opening reactions of the cyclopropylcarbinyl radical (leading to the 3-butenyl radical) and its mono-substituted analogues containing the methyl, ethyl, propyl, isopropyl, isobutyl, fluorine, chlorine, bromine, hydroxyl. methoxy, cyanogen, nitryl, vinyl, and phenyl substituents on the ring (leading to the pseudo-secondary and primary radicals, respectively). the enthalpies of activation, rate constants, and reaction enthalpies for all ring opening reactions were calculated. the predicted enthalpy of activation, rate constant, and reaction enthalpy of the cyclopropylcarbinyl radical ring opening reaction are in excellent agreement with the corresponding experimental values. for the alkyl (methyl, ethyl, propyl, isopropyl, and isobutyl) substitutions, steric effects are found to be the dominating factor to affect the ring opening reactions, while for the rest substitutions, the stereoelectronic effects play the most important roles. our calculations indicate that the cyanogen, nitryl, vinyl, and phenyl substituents, which contain pi bonds, have much larger effects on the ring opening reactions than the other substituents. (c) 2009 elsevier b.v. all rights reserved.
WOS关键词	POLARIZABLE CONTINUUM MODEL ; MOLECULAR-ORBITAL CALCULATIONS ; AB-INITIO ; KINETICS ; REARRANGEMENT ; DENSITY ; ENERGY ; CYCLOPROPYLMETHYL ; ALLYLCARBINYL ; HYDROXYLATION
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000274678800002
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2411263
专题	中国科学院大学
通讯作者	Chen, Bo-Zhen
作者单位	Chinese Acad Sci, Grad Univ, Coll Chem & Chem Engn, Beijing 100864, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Qing-Li,Chen, Bo-Zhen. Theoretical studies of the effects of substituents on the ring opening reactions for the cyclopropylcarbinyl radical[J]. Journal of molecular structure-theochem,2010,941(1-3):10-21.
APA	Zhang, Qing-Li,&Chen, Bo-Zhen.(2010).Theoretical studies of the effects of substituents on the ring opening reactions for the cyclopropylcarbinyl radical.Journal of molecular structure-theochem,941(1-3),10-21.
MLA	Zhang, Qing-Li,et al."Theoretical studies of the effects of substituents on the ring opening reactions for the cyclopropylcarbinyl radical".Journal of molecular structure-theochem 941.1-3(2010):10-21.

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