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Lindlar né Jonasson, Niko S. W., Menke, Annika, Senft, Laura, Squarcina, Andrea, Schmidl, David, Fisher, Katherine R., Demeshko, Serhiy, Kruse, Jan C., Josephy, Thomas, Mayer, Peter, Gutenthaler-Tietze, Jonathan, Comba, Peter, Meyer, Franc, Ivanović-Burmazović, Ivana and Daumann, Lena J. (2025) Two plus four equals three - iron(II)/iron(IV) comproportionation as an additional pathway for iron(IV)-oxido reactions. Inorganic Chemistry. pp. 1-16. ISSN 1520-510X
Iron enzymes are ubiquitous in nature. In particular, enzymes with iron−oxygen cofactors as active sites perform a vast variety of reactions. Both iron(III)-hydroxido and iron(IV)-oxido species have been observed to play a catalytically active role. In order to complement biochemical investigations, a large variety of synthetic compounds using these motifs were synthesized in past decades to study and understand their inherent reactivity. One such synthetic model complex is [FeIV(O)(Py5Me2)]2+, (Py5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine, henceforth labelled L1), which was used as a model complex for epigenetically relevant iron(II)/α-ketoglutarate-dependent ten-eleven translocation 5-methylcytosine dioxygenases (TET). Additionally, [FeIII(OH)(Py5(OH)2)]2+ (Py5(OH)2 =pyridine-2,6-diylbis [di(pyridin-2-yl)methanol, henceforth labelled L2) was tested as alipoxygenase model. We have complemented the available complexes of these related pentapyridyl complexes to include all oxidation states II−IV and performed detailed spectroscopic and spectrometric investigations. We found that iron(II) and iron(IV)-oxido compounds (cross-)comproportionate readily to form iron(III)-hydroxido species, which represents a major side reaction for model complex investigations. We also investigated the oxidative reactivity of a new iron(IV)-oxido complex.
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