DFT study on the catalytic decomposition of hydrogen peroxide by iron complexes of nitrilotriacetate

Abstract The Fenton system in the presence of nitrilotriacetate (NTA) ligand is studied by DFT approach. The calculations show that complexation of Fe(II) with NTA significantly facilitates the H 2 O 2 activation. The ferric‐hydroperoxo intermediate NTAFe(III)OOH predominantly decays via the disproportionation into NTAFe(II)OH 2 and NTAFe(IV)O involving the formation of a μ‐1,2‐hydroperoxo‐bridged biferric intermediate. In this mechanism, the bridged hydroperoxo is reduced by hydroperoxo ligand rather than by Fe(III). On the one hand, the NTAFe(III)OOH is sluggish to undergo hydrogen abstraction; on the other hand, it is a good nucleophile that may perform aldehyde deformylation. The present calculations suggest that both ˙OH and Fe(IV)O are generated in the NTA‐assisted Fenton system. However, the polycarboxylate ligand provides a favorable environment for H 2 O 2 to accumulate around iron ion through hydrogen bonding. This promotes the quenching of Fe(IV)O by H 2 O 2 , rationalizing why the Fe(IV)O species is hardly detected in the NTA‐assisted Fenton system.