Dürr KL, Olah J, Davydov R, Kleimann M, Li J, Lang N, Puchta R, Hübner E, Drewello T, Harvey JN, Jux N, Ivanovic-Burmazovic I (2010)
Publication Type: Journal article, Original article
Publication year: 2010
Original Authors: Duerr K., Olah J., Davydov R., Kleimann M., Li J., Lang N., Puchta R., Hübner E., Drewello T., Harvey J., Jux N., Ivanović-Burmazović I.
Publisher: Royal Society of Chemistry
Book Volume: 39
Pages Range: 2049-2056
Journal Issue: 8
DOI: 10.1039/b920237d
We demonstrate that a one electron reduced product of the heme iron dioxygen adduct exists in solution not only as the commonly accepted iron(iii)-peroxo species, but coexists with its isomeric iron(ii)-superoxo form. This unusual reduced metal-superoxide adduct [M(ii)-O] is recently reported as a reactive intermediate in the case of non-heme extradiol dioxygenases and could also be generated by cryoreduction of a heme Fe-O adduct. The existence of iron(ii)-superoxo species in solution is consistent with IR, EPR, mass and Mössbauer spectra. The equilibrium between heme iron(iii)-peroxo and iron(ii)-superoxo forms is supported by density functional theory and explains our previous finding that upon release of coordinated (su)peroxide a corresponding iron(ii) complex remains. These results shed new light on the nature of heme iron(iii)-peroxo species that are key intermediates in the metalloenzyme-catalyzed dioxygen and hydrogen peroxide activation. © 2010 The Royal Society of Chemistry.
APA:
Dürr, K.L., Olah, J., Davydov, R., Kleimann, M., Li, J., Lang, N.,... Ivanovic-Burmazovic, I. (2010). Studies on an iron(iii)-peroxo porphyrin. Iron(iii)-peroxo or iron(ii)-superoxo? Dalton Transactions, 39(8), 2049-2056. https://doi.org/10.1039/b920237d
MLA:
Dürr, Katharina L., et al. "Studies on an iron(iii)-peroxo porphyrin. Iron(iii)-peroxo or iron(ii)-superoxo?" Dalton Transactions 39.8 (2010): 2049-2056.
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