Theoretical Study on Chemospecificity of CF3SO3CF2CF3 + F− Reactions

Authors

  • Li Guo School of Data and Computer Science, Sun Yat-Sen University, Guangzhou, China
  • Yulong Xu School of Chemistry and Pharmaceutical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, Shandong 250353, China b.

DOI:

https://doi.org/10.4208/jams.102217.121217a

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 back- and 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 1031 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.

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Published

2018-07-10

Issue

Vol. 8 No. 3 (2017)

Section

Articles