Iron redox reactions hemerythrin

Peroxo-diiron(III) complexes can undergo not only redox but also ligand substitution reactions. Liberation of H202 was observed in the reactions with phenols and carboxylic acids leading also to the respective phenolate or carboxylate iron(III) complexes.86 Hydrolysis of a peroxo-diiron(III) complex results in an oxo-diiron(III) species and hydrogen peroxide. Such reaction is responsible for the autoxidation of hemerythrin, but is very slow for the native protein due to hydrophobic shielding of the active site (Section 4.2.3).20 The hydrolysis of iron(III) peroxides is reversible, and the reverse reaction, the formation of peroxo intermediates from H202 and the (di)iron(III), is often referred to as peroxide shunt and is much better studied for model complexes. 

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