DFT study on the reactions of ClO-/BrO- with RCl (R = CH3, C2H5, and C3H7) in gas phase
Gas-phase reactions of ClO-/BrO- with RCl (R = CH3, C2H5, and C3H7) have been investigated in detail using the popular DFT functional BHandHLYP/aug-cc-pVDZ level of theory. As a result, our findings strongly suggest that the type of reaction is firstly initiated by a typical S(N)2 fashion. Subsequently, two competitive substitution steps, named as S(N)2-induced substitution and S(N)2-induced elimination, respectively, would proceed before the initial S(N)2 product ion-dipole complex separates, in which the former exhibits less reactivity than the latter. Those are consistent with relevant experimental results. Moreover, we have also explored reactivity difference for the title reactions in term of some factors derived from methyl group, p-pi electronic conjugation, ionization energy (IE), as well as molecular orbital (MO) analysis.
anion clo-/bro- density functional theory (dft) mechanism