Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
9591020 | Journal of Molecular Structure: THEOCHEM | 2005 | 8 Pages |
Abstract
Gas-phase reaction of C(1)F3S(2)O2O(3)C(4)H2C(5)F3 and Fâ(16) is investigated using DFT method. The geometries of various stationary points and their relative energies are obtained from 6-31+G*, 6-311G**, and 6-311++G** levels. In the SN2(C) reaction leading to the cleavage of the C(4)-O(3) bond, the reaction complex results from attacking of Fâ at a hydrogen atom H11 attached to carbon atom C(4). Afterward, Fâ 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 SN2(C) reaction is irreversible. On the contrary, the SN2(S) reaction leading to the cleavage of the S(2)-O(3) bond is reversible, and it is initiated by attacking of Fâ at the atom S(2) from the backside of the atom O(3). The products of the reaction CF3SO3CH2CF3 +Fâ should be, thermodynamically, controlled due to the reversibility of the SN2(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 SN2(C) reaction.
Keywords
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Li Guo, Zhong-Heng Yu, Shi-Zheng Zhu, Qing-Yun Chen,