title: Hydrogenation of simple aromatic molecules: a computational study of the mechanism.
abstract: Quantum chemistry calculations have been used to study the metal-free hydrogenation reactions of a variety of simple aromatic, heteroaromatic, and related linear conjugated systems. We find that the barrier for uncatalyzed 1,4-hydrogenation is always substantially lower (by approximately 200 kJ mol-1) than that for 1,2-hydrogenation, despite similar reaction enthalpies. The presence of hydrogen fluoride as a catalyst is found to decrease the 1,2-hydrogenation barriers but, in most cases, to slightly increase the 1,4-hydrogenation barriers when a constrained geometric arrangement is employed. These qualitative observations are consistent with orbital symmetry considerations, which show that both the uncatalyzed 1,4-hydrogenation and the catalyzed 1,2-hydrogenation are formally symmetry-allowed processes. An extreme example of the catalyzed 1,2-hydrogenation of benzene is provided by the involvement of a second molecule of hydrogen, which leads to a substantial lowering of the barrier. The effect of catalysis was further investigated by applying a selection of additional catalysts to the 1,2- and 1,4-hydrogenation of benzene. A decreasing barrier with increasing catalyst acidity is generally observed for the catalytic 1,2-hydrogenation, but the situation is more complex for catalytic 1,4-hydrogenation. For the uncatalyzed 1,4-hydrogenation of aromatic systems containing one or more nitrogen heteroatoms, the barriers for [C,C], [C,N], and [N,N] hydrogenations are individually related to the reaction enthalpies by the Bell-Evans-Polanyi principle. In addition, for a given reaction enthalpy, the barriers for [C,C] hydrogenation are generally lower than those for [C,N] or [N,N] hydrogenation. Finally, we find that the distortion experienced by the reactants in forming the transition structure represents a secondary factor that influences the reaction barrier. The correlation between these quantities allows the 1,4-hydrogenation barriers to be predicted from a ground-state property.
authors.affiliation: School of Chemistry and Centre of Excellence in Free Radical Chemistry and Biotechnology, University of Sydney, Sydney, NSW 2006, Australia.
authors.forename: George
authors.initials: G
authors.lastname: Zhong
authors.forename: Bun
authors.initials: B
authors.lastname: Chan
authors.forename: Leo
authors.initials: L
authors.lastname: Radom
mesh_terms: D002384:Catalysis; D003198:Computer Simulation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006865:Hydrogenation; D011789:Quantum Theory
chemical_list: D006841:Hydrocarbons, Aromatic; D006859:Hydrogen