Front-Side SN2 Reaction, CF3SO3CF2CF3＋F－, Leading to the C—O Cleavage

Acta Chimica Sinica ›› 2005, Vol. 63 ›› Issue (10): 897-902. Previous Articles Next Articles

Original Articles

全氟烷基磺酸酯C—O键断裂的同面S_N2反应

郭丽¹，虞忠衡*¹，朱士正²，陈庆云²

(¹中国科学院化学研究所分子动态和稳态国家重点实验室北京 100080)
(²中国科学院上海有机化学研究所上海 200032)

投稿日期:2004-09-13 修回日期:2005-01-25 发布日期:2010-12-10
通讯作者: 虞忠衡

Front-Side S_N2 Reaction, CF₃SO₃CF₂CF₃＋F^－, Leading to the C—O Cleavage

GUO Li¹, YU Zhong-Heng*¹, ZHU Shi-Zheng², CHEN Qing-Yun²

(¹ State Key Laboratory for Structural Chemistry of Unstable & Stable Species, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100080)
(² Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032)

Received:2004-09-13 Revised:2005-01-25 Published:2010-12-10
Contact: YU Zhong-Heng

Abstract

The front-side S_N2 reaction, CF₃SO₃CF₂CF₃＋F^－, leading to the C—O cleavagewas studied using DFT. The reactant complex, transition state, product complex and products, including their vibration frequencies, were optimized and calculated at B3LYP/6-311G** level. The potential energy surface for the front-side S_N2 reaction was investigated, showing that the front-side S_N2 mechanism is possible. However, as shown by computation, the products are thermodynamically controlled, and the S—O cleavage is predominates over the C—O cleavage. As a result, it is difficult for the products resulting from the C—O cleavage to be detected experimentally. Meanwhile, the neighboring effect of the —CF₃ group on the front-side S_N2 mechanism was found.

Key words: reaction mechanism, DFT method, perfluorosulfonate, the front-side S_N2 reaction

Cite this article

GUO Li, YU Zhong-Heng*, ZHU Shi-Zheng², CHEN Qing-Yun². Front-Side S_N2 Reaction, CF₃SO₃CF₂CF₃＋F^－, Leading to the C—O Cleavage[J]. Acta Chimica Sinica, 2005, 63(10): 897-902.

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全氟烷基磺酸酯C—O键断裂的同面S_N2反应

Front-Side S_N2 Reaction, CF₃SO₃CF₂CF₃＋F^－, Leading to the C—O Cleavage

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全氟烷基磺酸酯C—O键断裂的同面SN2反应