Open AccessComparative Computational Study of Hydrogen Abstraction Reactions of CY 3 H + XO − (X, Y = F, Cl, and Br)
Author(s) -
Junxi Liang,
Qiong Su,
Dezhi Zhao,
Yanbin Wang,
Guihua Li,
Zhiyuan Geng
Publication year - 2016
Publication title -
heteroatom chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.283
H-Index - 42
eISSN - 1098-1071
pISSN - 1042-7163
DOI - 10.1002/hc.21317
Subject(s) - chemistry , reactivity (psychology) , halogen , hydrogen atom abstraction , density functional theory , computational chemistry , hydrogen , reaction rate constant , basis set , transition state , medicinal chemistry , reaction mechanism , kinetics , organic chemistry , catalysis , medicine , alkyl , alternative medicine , physics , pathology , quantum mechanics
Abstract The effects of halogen substituents on the reactivity are characterized by the hybrid B3LYP and BHandHLYP functionals of density functional theory using the aug‐cc‐pVDZ basis set. The species XO − and CY 3 H, where X, Y = F, Cl, and Br, have been chosen as model reactants in this work. Also, the mechanism of the hydrogen abstraction (HAT) reaction has been used to study the chemical reactivity of these anionic reactions. Our theoretical findings suggest that the relative reactivity of the CY 3 H + XO − reactions increases as Y goes from F to Br and decreases as X goes from F to Br. Moreover, among all reactions investigated in this study, the special role of the Y has very dominant effect on activation of the C–H bond in CY 3 H when XO − attacks the CY 3 H. Again, through the transition state theory the rate constants at 298–1000 K are also evaluated for the HAT reactions, indicating the lower the temperature the faster is the chemical reaction.