Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework
Issued Date
2023-11-01
Resource Type
ISSN
00368075
eISSN
10959203
Scopus ID
2-s2.0-85176375058
Pubmed ID
37917685
Journal Title
Science
Volume
382
Issue
6670
Start Page
547
End Page
553
Rights Holder(s)
SCOPUS
Bibliographic Citation
Science Vol.382 No.6670 (2023) , 547-553
Suggested Citation
Hou K., Börgel J., Jiang H.Z.H., SantaLucia D.J., Kwon H., Zhuang H., Chakarawet K., Rohde R.C., Taylor J.W., Dun C., Paley M.V., Turkiewicz A.B., Park J.G., Mao H., Zhu Z., Ercan Alp E., Zhao J., Hu M.Y., Lavina B., Peredkov S., Lv X., Oktawiec J., Meihaus K.R., Pantazis D.A., Vandone M., Colombo V., Bill E., Urban J.J., David Britt R., Grandjean F., Long G.J., DeBeer S., Neese F., Reimer J.A., Long J.R. Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework. Science Vol.382 No.6670 (2023) , 547-553. 553. doi:10.1126/science.add7417 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/91429
Title
Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework
Author(s)
Hou K.
Börgel J.
Jiang H.Z.H.
SantaLucia D.J.
Kwon H.
Zhuang H.
Chakarawet K.
Rohde R.C.
Taylor J.W.
Dun C.
Paley M.V.
Turkiewicz A.B.
Park J.G.
Mao H.
Zhu Z.
Ercan Alp E.
Zhao J.
Hu M.Y.
Lavina B.
Peredkov S.
Lv X.
Oktawiec J.
Meihaus K.R.
Pantazis D.A.
Vandone M.
Colombo V.
Bill E.
Urban J.J.
David Britt R.
Grandjean F.
Long G.J.
DeBeer S.
Neese F.
Reimer J.A.
Long J.R.
Börgel J.
Jiang H.Z.H.
SantaLucia D.J.
Kwon H.
Zhuang H.
Chakarawet K.
Rohde R.C.
Taylor J.W.
Dun C.
Paley M.V.
Turkiewicz A.B.
Park J.G.
Mao H.
Zhu Z.
Ercan Alp E.
Zhao J.
Hu M.Y.
Lavina B.
Peredkov S.
Lv X.
Oktawiec J.
Meihaus K.R.
Pantazis D.A.
Vandone M.
Colombo V.
Bill E.
Urban J.J.
David Britt R.
Grandjean F.
Long G.J.
DeBeer S.
Neese F.
Reimer J.A.
Long J.R.
Author's Affiliation
Berkeley College of Chemistry
Miller Institute for Basic Research in Science
Center for Advanced Radiation Sources
Max Planck Institute for Chemical Energy Conversion
Korea Advanced Institute of Science and Technology
Università degli Studi di Milano
University of California, Berkeley
Missouri University of Science and Technology
Max Planck Institute for Coal Research
University of California, Davis
Mahidol University
Northwestern University
Lawrence Berkeley National Laboratory
The Advanced Photon Source
Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM)
Miller Institute for Basic Research in Science
Center for Advanced Radiation Sources
Max Planck Institute for Chemical Energy Conversion
Korea Advanced Institute of Science and Technology
Università degli Studi di Milano
University of California, Berkeley
Missouri University of Science and Technology
Max Planck Institute for Coal Research
University of California, Davis
Mahidol University
Northwestern University
Lawrence Berkeley National Laboratory
The Advanced Photon Source
Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM)
Other Contributor(s)
Abstract
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 O2 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 a-ketoglutarate-dependent dioxygenases. The framework reacts with O2 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 Kb x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O2, the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.