Theoretical study on the reaction of hydrogen atoms with aniline

The reaction of aniline with hydrogen atom is investigated herein using the hybrid meta-DFT functional of BB1 K. Hydrogen atom is found to preferentially add at an ortho position. However, the fate of the o -(C 6 H 5 NH 2 )H adduct is found to be solely the deactivation of the initial addition channel. The rate constant for the abstraction channel (C 6 H 5 NH 2 + H → C 6 H 5 NH + H 2 ) is fitted by the expression 1.10 × 10 −11 exp(−4,200/ T ) cm 3 molecule −1 s −1 . Our calculated rate constant for the abstraction channel agrees very well with the available experimental measurements. Satisfactory agreement is found between calculated and experimental measurements for the displacement channel (C 6 H 5 NH 2 + H → C 6 H 6 + NH 2 ). Our detailed analysis for the corresponding displacements in toluene and phenol suggests that the three systems exhibit similar behavior with regard to the relative importance of abstraction and displacement channels.