Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5395338 | Computational and Theoretical Chemistry | 2011 | 6 Pages |
Abstract
The ion/molecule reactions of CH2NO2- with CCl4 and CHCl3 in gas phase have been theoretically investigated using BH&HLYP, B3LYP and MP2 methods with 6-31+Gâ and 6-311+Gââ basis sets. The experimentally observed H/Cl exchange reaction between CH2NO2- and CCl4 was found to include two individual reactions, the chlorine cation transferring from CCl4 to CH2NO2- via a chlorine-attack transition state and the proton transferring from CH2ClNO2 to CCl3- via a proton-attack transition state. The calculated energies indicate that the H/Cl exchange is both kinetically and thermodynamically favorable. The H/Cl exchange reaction was found to be also possible for CHCl3, but a notable activation barrier represented by a bridge-like transition state and strong endothermicity for the chlorine cation-transfer step make this reaction impossible under low-energy condition. The classic SN2 reactions between CH2NO2- and the two chloromethanes were also calculated and notable energy barriers were identified for them.
Keywords
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Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Tao Hong Li, Chuan Ming Wang, Shi Wen Yu, Xiao Guang Xie,