Theoretical studies of the effects of substituents on the ring opening reactions for the cyclopropylcarbinyl radical
文献类型：期刊论文
| 作者 | Zhang, Qing-Li; Chen, Bo-Zhen |
| 刊名 | Journal of molecular structure-theochem
 |
| 出版日期 | 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 |
| WOS记录号 | WOS:000274678800002 |
| 出版者 | ELSEVIER SCIENCE BV |
| URI标识 | http://www.irgrid.ac.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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来源：中国科学院大学
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