Mechanism of H_2O_2 Dismutation Catalyzed by a New Catalase Mimic(a Non-Heme Dibenzotetraaza[14]annulene-Fe(lll)Complex):A Density Functional Theory Investigation

摘要

The mechanism of H_2O_2 dismutation catalyzed by the dibenzotetraaza[14]annulene-Fe(lll)complex([Fe(C_(24)H_(22)N_40_4)]~+)which was recently reported(Paschke,J.;Kirsch,M.;Korth,H.G.;de Groot,H.;Sustmann,R.J.Am.Chem.Soc.2001,123,11099)has been investigated by density functional theory using the B3LYP hybrid functional.The quartet potential energy profile of the catalytic reaction has been explored.In the whole catalytic cycle,the rate-determining step is found to be the 0-0 bond homolytic cleavage,without the assistance of solvent molecules in the second coordination shell.The calculated free energy barrier for this step is 10.8 kcal/mol,which is in reasonable agreement with the experimental facts.The calculations also show that the hydroxyl and hydroperoxyl radicals may be generated in the reaction processes,but they can be efficiently quenched in strongly exothermic steps.This study provides a satisfactory explanation to the observed efficiency of the H_2O_2 dismutation catalyzed by this complex.