Ferric Heme Superoxide Reductive Transformations to Ferric Heme (Hydro)Peroxide Species: Spectroscopic Characterization and Thermodynamic Implications for H-Atom Transfer (HAT)
Hyun Kim
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Patrick J. Rogler
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Savita K. Sharma
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Andrew W. Schaefer
Chemistry Department, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Dr. Edward I. Solomon
Chemistry Department, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Dr. Kenneth D. Karlin
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorHyun Kim
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Patrick J. Rogler
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Savita K. Sharma
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorDr. Andrew W. Schaefer
Chemistry Department, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Dr. Edward I. Solomon
Chemistry Department, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Dr. Kenneth D. Karlin
Chemistry Department, Johns Hopkins University, Baltimore, MD, 21218 USA
Search for more papers by this authorAbstract
A new end-on low-spin ferric heme peroxide, [(PIm)FeIII−(O22−)]− (PIm-P), and subsequently formed hydroperoxide species, [(PIm)FeIII−(OOH)] (PIm-HP) are generated utilizing the iron-porphyrinate PIm with its tethered axial base imidazolyl group. Measured thermodynamic parameters, the ferric heme superoxide [(PIm)FeIII−(O2⋅−)] (PIm-S) reduction potential (E°′) and the PIm-HP pKa value, lead to the finding of the OO−H bond-dissociation free energy (BDFE) of PIm-HP as 69.5 kcal mol−1 using a thermodynamic square scheme and Bordwell relationship. The results are validated by the observed oxidizing ability of PIm-S via hydrogen-atom transfer (HAT) compared to that of the F8 superoxide complex, [(F8)FeIII−(O2.−)] (S) (F8=tetrakis(2,6-difluorophenyl)porphyrinate, without an internally appended axial base imidazolyl), as determined from reactivity comparison of superoxide complexes PIm-S and S with the hydroxylamine (O-H) substrates TEMPO-H and ABNO-H.
Conflict of interest
The authors declare no conflict of interest.
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