The anionic chain process mechanism for reactions of perchlorofluoroethanes with nucleophiles in solution: a theoretical study
文献类型：期刊论文
| 作者 | Zhang, Cheng-Gen; Huang, Ming-Bao |
| 刊名 | Journal of physical organic chemistry
 |
| 出版日期 | 2007 |
| 卷号 | 20期号:1页码:65-71 |
| 关键词 | Perchlorofluoroethanes Nucleophiles Anionic chain process mechanism Chlorophilic attack Anionic hyperconjugation Solvent effects Dft b3lyp Scipcm model |
| ISSN号 | 0894-3230 |
| DOI | 10.1002/poc.1128 |
| 通讯作者 | Huang, ming-bao(mbhuang1@gucas.ac.cn) |
| 英文摘要 | Anionic chain process mechanism (including reactions (1)-(4)) suggested by the experimental investigations for the reactions of nucleophile (ch3o-) with perchlorofluoroethanes cf2clccl3 (1), cf2clccl2f (2), and cf3ccl3 (3) in solution is examined by performing calculations using the b3lyp method and the scipcm (self-consistent isodensity polarizable continuum) model for simulating solution effects. the scipcm-b3lyp calculations indicate that anionic species have large solvation energies and solvation energy values for different kinds of anions are quite different, which effects changes in delta h's for the reactions in solution. competition between anionic hyperconjugation and solvation leads to negative delta h values for reactions (2) from 1 and 2 in solution. reactions (3) and (4) from 1, 2, and 3 in solution are predicted to be exothermic or highly exothermic. since the delta h values for reactions (1) and (2) from 1 and 2 in solution are negative or small positive values, the reactions of ch3o- with 1 and 2 in solution proceed via the anionic chain process. for 3 in solution, reactions (1) and (2) are endothermic while reactions (3) and (4) are exothermic or highly exothermic. the reactions of ch3o- with 3 in solution may proceed via the anionic chain process. all these conclusions are in agreement with the experimental indications for reactions of nucleophiles with 1, 2, and 3 in solution. copyright (c) 2007 john wiley & sons, ltd. |
| WOS关键词 | HYPERCONJUGATION ; ATTACKS ; DENSITY |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Organic ; Chemistry, Physical |
| 语种 | 英语 |
| WOS记录号 | WOS:000245112800008 |
| 出版者 | WILEY-BLACKWELL |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2383911 |
| 专题 | 中国科学院大学 |
| 通讯作者 | Huang, Ming-Bao |
| 作者单位 | Grad Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhang, Cheng-Gen,Huang, Ming-Bao. The anionic chain process mechanism for reactions of perchlorofluoroethanes with nucleophiles in solution: a theoretical study[J]. Journal of physical organic chemistry,2007,20(1):65-71. |
| APA | Zhang, Cheng-Gen,&Huang, Ming-Bao.(2007).The anionic chain process mechanism for reactions of perchlorofluoroethanes with nucleophiles in solution: a theoretical study.Journal of physical organic chemistry,20(1),65-71. |
| MLA | Zhang, Cheng-Gen,et al."The anionic chain process mechanism for reactions of perchlorofluoroethanes with nucleophiles in solution: a theoretical study".Journal of physical organic chemistry 20.1(2007):65-71. |
入库方式： iSwitch采集
来源：中国科学院大学
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。