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Intermediates and the enzyme-product complex observed in different subunits of the homotetrameric [Fe-HPCD(4NC)] enzyme-substrate complex contained within the asymmetric unit of the enzyme crystal after reacting with O2 (PDB 2IGA, 1.95 Å) [14]. Structures of (A) [Fe-HPCD(4NSQ•)superoxo] exhibiting substrate ring puckering at C2, suggesting a localized semiquinone substrate radical, (B) the [Fe-HPCD-alkylperoxo] intermediate, and (C) the enzyme-product complex.
