DFT study on the reaction mechanisms of polyfluorosulfonate ester with F-
文献类型：期刊论文
| 作者 | Li, G; Yu, ZH; Zhu, SZ; Chen, QY |
| 刊名 | JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
 |
| 出版日期 | 2005-10-07 |
| 卷号 | 730期号:1-3页码:143-150 |
| 关键词 | Polyfluoroalkylsulfonate s(n)2 Reactions Dft Method Chemospecific Reaction |
| ISSN号 | 0166-1280 |
| DOI | 10.1016/j.theochem.2005.06.013 |
| 英文摘要 | Gas-phase reaction of Q(1)F3S(2)O2O(3)Q4)H2C((5))F-3 and F-(16) is investigated using DIFT method. The geometries of various stationary points and their relative energies are obtained from 6-31 + G*, 6-31 1G**, and 6-311 + + G** levels. In the S(N)2(C) reaction leading to the cleavage of the C(4)-O(3) bond, the reaction complex results from attacking of F- at a hydrogen atom H11 attached to carbon atom C(4). Afterward, F- is attacking the atom C(4) from the backside of the atom O(3) with the help of the neighboring effect, and meanwhile a multi-membered ring, F(16)-H(11)-C(4)-C(5)-F(16), is being formed. The S(N)2(C) reaction is irreversible. On the contrary, the S(N)2(S) reaction leading to the cleavage of the S(2)-O(3) bond is reversible, and it is initiated by attacking of F- at the atom S(2) from the backside of the atom O(3). The products of the reaction CF3SO3CH2CF3 +F- should be, thermodynamically, controlled due to the reversibility of the S(N)2(S) reaction, and those result, chemospecifically, from the cleavage of the C-O bond. At last, the SCRF calculations confirm that the solvent effect is preferable to the S(N)2(C) reaction. (c) 2005 Elsevier B.V. All rights reserved. |
| 语种 | 英语 |
| WOS记录号 | WOS:000232320900017 |
| 出版者 | ELSEVIER SCIENCE BV |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/56393]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Yu, ZH |
| 作者单位 | 1.Chinese Acad Sci, State Key Lab Struct Chem Unstable & Stable Speci, Inst Chem, Beijing 100080, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai 200031, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, G,Yu, ZH,Zhu, SZ,et al. DFT study on the reaction mechanisms of polyfluorosulfonate ester with F-[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2005,730(1-3):143-150. |
| APA | Li, G,Yu, ZH,Zhu, SZ,&Chen, QY.(2005).DFT study on the reaction mechanisms of polyfluorosulfonate ester with F-.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,730(1-3),143-150. |
| MLA | Li, G,et al."DFT study on the reaction mechanisms of polyfluorosulfonate ester with F-".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 730.1-3(2005):143-150. |
入库方式： OAI收割
来源：化学研究所
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