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Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV)=O species remains an unrealized goal. Here...

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Published in:Science (American Association for the Advancement of Science) 2023-11, Vol.382 (6670), p.547-553
Main Authors: Hou, Kaipeng, Börgel, Jonas, Jiang, Henry Z. H., SantaLucia, Daniel J., Kwon, Hyunchul, Zhuang, Hao, Chakarawet, Khetpakorn, Rohde, Rachel C., Taylor, Jordan W., Dun, Chaochao, Paley, Maria V., Turkiewicz, Ari B., Park, Jesse G., Mao, Haiyan, Zhu, Ziting, Alp, E. Ercan, Zhao, Jiyong, Hu, Michael Y., Lavina, Barbara, Peredkov, Sergey, Lv, Xudong, Oktawiec, Julia, Meihaus, Katie R., Pantazis, Dimitrios A., Vandone, Marco, Colombo, Valentina, Bill, Eckhard, Urban, Jeffrey J., Britt, R. David, Grandjean, Fernande, Long, Gary J., DeBeer, Serena, Neese, Frank, Reimer, Jeffrey A., Long, Jeffrey R.
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Language:English
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Summary:In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV)=O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O 2 at low temperatures to form high-spin iron(IV)=O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O 2 , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol. Redox-active metalloproteins are often adept at binding to and controlling the reactivity of oxygen. Hou et al . showed that a metal-organic framework can similarly activate dioxygen and perform hydroxylation of aliphatic substrates. The authors used a range of spectroscopic techniques to demonstrate that the mechanism proceeds through a high-spin iron(IV) oxo species, similar to what is seen in some dioxygenase enzymes. This system can perform catalytic oxygenation of cyclohexane and should inspire future catalyst development for dioxygen activation and hydrocarbon oxidation. —Michael A. Funk A metal organic framework that mimics non-heme iron dioxygenase enzymes performs hydrocarbon oxidation.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.add7417