Abstract
Binuclear non-heme iron enzymes activate O2 to perform diverse chemistries. Three different structural mechanisms of O2 binding to a coupled binuclear iron site have been identified utilizing variable-temperature, variable-field magnetic circular dichroism spectroscopy (VTVH MCD). For the μ-OH-bridged Fe(II)2 site in hemerythrin, O2 binds terminally to a five-coordinate Fe(II) center as hydroperoxide with the proton deriving from the μ-OH bridge and the second electron transferring through the resulting μ-oxo superexchange pathway from the second coordinatively saturated Fe(II) center in a proton-coupled electron transfer process. For carboxylate-only-bridged Fe(II)2 sites, O2 binding as a bridged peroxide requires both Fe(II) centers to be coordinatively unsaturated and has good frontier orbital overlap with the two orthogonal O2 π* orbitals to form peroxo-bridged Fe(III)2 intermediates. Alternatively, carboxylate-only-bridged Fe(II)2 sites with only a single open coordination position on an Fe(II) enable the one-electron formation of Fe(III)–O2 − or Fe(III)–NO− species. Finally, for the peroxo-bridged Fe(III)2 intermediates, further activation is necessary for their reactivities in one-electron reduction and electrophilic aromatic substitution, and a strategy consistent with existing spectral data is discussed.
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Acknowledgments
EIS thanks Prof. J. Martin Bollinger and Prof. Carsten D. Krebs (Penn State U), Prof. Brian G. Fox (U of Wisconsin-Madison), Prof. Donald M. Kurtz Jr. (U of Texas at San Antonio), Prof. John D. Lipscomb (U of Minnesota), Prof. Elizabeth C. Theil (Children’s Hospital Oakland Research Institute and North Carolina State U), Prof. Lawrence Que, Jr. (U of Minnesota), and past graduate students and postdocs for their major contributions to these studies. This work was supported by the National Science Foundation (MCB1404866 to EIS), National Institutes of Health (GM040392 to EIS), C1 Gas Refinery Program through the National Research Foundation of Korea (2015M3D3A1A01064889 to KP), and Korea Institute of Science and Technology Information (KSC-2015-C1-030 to KP).
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Solomon, E.I., Park, K. Structure/function correlations over binuclear non-heme iron active sites. J Biol Inorg Chem 21, 575–588 (2016). https://doi.org/10.1007/s00775-016-1372-9
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DOI: https://doi.org/10.1007/s00775-016-1372-9