Computational study on reaction mechanisms and kinetics of RNCN (R = H, F, Cl, Br, CH3) radicals with NO.
We carried out a computational study of radical reactions of RNCN (R = H, F, Cl, Br, CH(3)) + NO to investigate how the substitution can influence their corresponding energy barriers and rate coefficients. The preferable reactive sites of RNCN radicals with various substituents are calculated by employing the Fukui functions and hard-and-soft acid-and-base theory, which were generally proved to be successful in the prediction and interpretation of regioselectivity in various types of electrophilic and nucleophilic reactions. Our calculated results clearly show that if the substituted RNCN radical has electron-donating substituent (for R = CH(3)), its corresponding barrier heights for transition states will be substantially decreased. The possible explanations of the observed increase and/or decrease in the energy barriers for the varied substituted RNCN radicals are also analyzed in this article.
Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei, 111, Taiwan. chl3@faculty.pccu.edu.tw
Hui-Lung
HL
Chen
Sheng-ke
SK
Wu
Yu-Huan
YH
Lu