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. Author manuscript; available in PMC: 2008 Nov 21.

Published in final edited form as: J Am Chem Soc. 2007 Oct 30;129(46):14500–14510. doi: 10.1021/ja076121h

Speciation plot for reaction of diiron(II) ToMOH:2ToMOD with dioxygen. Reduced diiron(II) protein ( ) reacts with dioxygen at ~ 26 s⁻¹ to form a diiron(III) transient species ( ). Only ~45% of diiron(II) clusters give rise to this intermediate. The diiron(III) transient subsequently decays to the oxidized resting state ( ) at ~ 0.045 s⁻¹. The unreacted diiron(II) centers decay slowly at 0.02 s⁻¹ to generate several ill-defined ferric species, the production of which is not depicted. Solid lines are one- or two-exponential fits to the data.

Inline graphic — Speciation plot for reaction of diiron(II) ToMOH:2ToMOD with dioxygen. Reduced diiron(II) protein ( ) reacts with dioxygen at ~ 26 s⁻¹ to form a diiron(III) transient species ( ). Only ~45% of diiron(II) clusters give rise to this intermediate. The diiron(III) transient subsequently decays to the oxidized resting state ( ) at ~ 0.045 s⁻¹. The unreacted diiron(II) centers decay slowly at 0.02 s⁻¹ to generate several ill-defined ferric species, the production of which is not depicted. Solid lines are one- or two-exponential fits to the data.