Effect of Redox Potential on Diiron-Mediated Disproportionation of Hydrogen Peroxide

Heme and nonheme dimanganese catalases are widely distributed in living organisms to participate in antioxidant defenses that protect biological systems from oxidative stress. The key step in these processes is the disproportionation of H₂O₂ to O₂ and water, which can be interpreted via two different mechanisms, namely via the formation of high-valent oxoiron(IV) and peroxodimanganese(III) or diiron(III) intermediates. In order to better understand the mechanism of this important process, we have chosen such synthetic model compounds that can be used to map the nature of the catalytically active species and the factors influencing their activities. Our previously reported μ-1,2-peroxo-diiron(III)-containing biomimics are good candidates, as both proposed reactive intermediates (Fe^IVO and Fe^III₂(μ-O₂)) can be derived from them. Based on this, we have investigated and compared five heterobidentate-ligand-containing model systems including the previously reported and fully characterized [Fe^II(L^1-4)₃]²⁺ (L¹ = 2-(2'-pyridyl)-1H-benzimidazole, L² = 2-(2'-pyridyl)-N-methyl-benzimidazole, L³ = 2-(4-thiazolyl)-1H-benzimidazole and L⁴ = 2-(4'-methyl-2'-pyridyl)-1H-benzimidazole) and the novel [Fe^II(L⁵)₃]²⁺ (L⁵ = 2-(1H-1,2,4-triazol-3-yl)-pyridine) precursor complexes with their spectroscopically characterized μ-1,2-peroxo-diiron(III) intermediates. Based on the reaction kinetic measurements and previous computational studies, it can be said that the disproportionation reaction of H₂O₂ can be interpreted through the formation of an electrophilic oxoiron(IV) intermediate that can be derived from the homolysis of the O-O bond of the forming μ-1,2-peroxo-diiron(III) complexes. We also found that the disproportionation rate of the H₂O₂ shows a linear correlation with the Fe^III/Fe^II redox potential (in the range of 804 mV-1039 mV vs. SCE) of the catalysts controlled by the modification of the ligand environment. Furthermore, it is important to note that the two most active catalysts with L³ and L⁵ ligands have a high-spin electronic configuration.