CF_3SO_3CF_2CF_3 + F^{−}反应化学特异性的理论研究

Journal of Atomic and Molecular Sciences Pub Date : 2018-02-01 DOI:10.4208/JAMS.102217.121217A

Li Guo, Yulong Xu

{"title":"CF_3SO_3CF_2CF_3 + F^{−}反应化学特异性的理论研究","authors":"Li Guo, Yulong Xu","doi":"10.4208/JAMS.102217.121217A","DOIUrl":null,"url":null,"abstract":"DFT and ab initio methods are used to investigate why the reaction, C(1)F3S(2)O2O(3)C(4)F2C(5)F3 + F − , results in the S-O cleavage chemospecifically. Three SN2 channels, i.e. S-O cleavage and backand frontside of C-O scission are predicted to occur. The F(11)and F(12) atoms of the C(4)F2 group play the multiple roles in three paths. Multi-membered rings are formed in C-O rupture mechanisms due to the neighboring effect. The rate of S-O scission reaction is 10 31 time as large as the rates of C-O rupture reactions. It is the combination of the irreversibility and the huge rate ratios to determine that S-O cleavage is chemospecific. This conclusion agrees well with the experimental results.","PeriodicalId":15131,"journal":{"name":"Journal of Atomic and Molecular Sciences","volume":"71 1","pages":"146-151"},"PeriodicalIF":0.0000,"publicationDate":"2018-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical study on chemospecificity of CF_3SO_3CF_2CF_3 + F^{−} reactions\",\"authors\":\"Li Guo, Yulong Xu\",\"doi\":\"10.4208/JAMS.102217.121217A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"DFT and ab initio methods are used to investigate why the reaction, C(1)F3S(2)O2O(3)C(4)F2C(5)F3 + F − , results in the S-O cleavage chemospecifically. Three SN2 channels, i.e. S-O cleavage and backand frontside of C-O scission are predicted to occur. The F(11)and F(12) atoms of the C(4)F2 group play the multiple roles in three paths. Multi-membered rings are formed in C-O rupture mechanisms due to the neighboring effect. The rate of S-O scission reaction is 10 31 time as large as the rates of C-O rupture reactions. It is the combination of the irreversibility and the huge rate ratios to determine that S-O cleavage is chemospecific. This conclusion agrees well with the experimental results.\",\"PeriodicalId\":15131,\"journal\":{\"name\":\"Journal of Atomic and Molecular Sciences\",\"volume\":\"71 1\",\"pages\":\"146-151\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2018-02-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Atomic and Molecular Sciences\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.4208/JAMS.102217.121217A\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Atomic and Molecular Sciences","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.4208/JAMS.102217.121217A","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}

引用次数: 0

摘要

采用DFT和从头算方法研究了C(1)F3S(2)O2O(3)C(4)F2C(5)F3 + F−导致S-O化学特异性裂解的原因。预测SN2有3个通道，即S-O裂解和C-O前后裂解。C(4)F2基团的F(11)和F(12)原子在三个路径中起着多重作用。在C-O断裂机制中，由于邻近效应形成了多元环。S-O断裂反应速率是C-O断裂反应速率的10 - 31倍。正是不可逆性和巨大的速率比的结合决定了S-O裂解具有化学特异性。这一结论与实验结果吻合较好。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Theoretical study on chemospecificity of CF_3SO_3CF_2CF_3 + F^{−} reactions

DFT and ab initio methods are used to investigate why the reaction, C(1)F3S(2)O2O(3)C(4)F2C(5)F3 + F − , results in the S-O cleavage chemospecifically. Three SN2 channels, i.e. S-O cleavage and backand frontside of C-O scission are predicted to occur. The F(11)and F(12) atoms of the C(4)F2 group play the multiple roles in three paths. Multi-membered rings are formed in C-O rupture mechanisms due to the neighboring effect. The rate of S-O scission reaction is 10 31 time as large as the rates of C-O rupture reactions. It is the combination of the irreversibility and the huge rate ratios to determine that S-O cleavage is chemospecific. This conclusion agrees well with the experimental results.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Journal of Atomic and Molecular Sciences PHYSICS, ATOMIC, MOLECULAR & CHEMICAL-

自引率

0.00%

发文量