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Dioxygen binding to the enzyme–substrate complex and O–O bond cleavage. (A) A ferric superoxo (E•S•O2)I or ferrous substrate radical (E•S•O2)II (30 to 50 s), (B) alkylperoxo (E•S•O2)III (1 min), and (C) seven-membered lactone (E•Int)II (3 to 5 min). The light blue 2Fobs – Fcalc maps and green Fobs – Fcalc omit maps are contoured at 1.0 σ and 3.0 σ, respectively. Atom color code: gray, carbon (protein residues); yellow, carbon (ligand); blue, nitrogen; red, oxygen; magenta, iron.
