Theoretical study of charge-remote fragmentation along the reaction coordinate of 1,4-hydrogen elimination in the gas-phase: Energy barrier and mechanism

Abstract

Density functional and Møller-Plesset perturbation approaches were applied to charge-remote fragmentation along the reaction coordinate of 1,4-hydrogen eliminations in the gas-phase. The mechanisms and energy barriers of the reactions are discussed. The calculations indicate that 1,4-hydrogen elimination via an aromatic-like six-atom transition state structure is energetically favorable with no involvement of the charge site. Cleavage of CC and CH bonds and the formation of HH bonds occur simultaneously, and the energy barrier of this reaction is 4.01 eV. Energy decomposition analysis predicts a repulsive interaction between the formed H2 and the remaining substituents.