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

Kaipeng Hou; Jonas Börgel; Henry Z H Jiang; Daniel J SantaLucia; Hyunchul Kwon; Hao Zhuang; Khetpakorn Chakarawet; Rachel C Rohde; Jordan W Taylor; Chaochao Dun; Maria V Paley; Ari B Turkiewicz; Jesse G Park; Haiyan Mao; Ziting Zhu; E Ercan Alp; Jiyong Zhao; Michael Y Hu; Barbara Lavina; Sergey Peredkov; Xudong Lv; Julia Oktawiec; Katie R Meihaus; Dimitrios A Pantazis; Marco Vandone; Valentina Colombo; Eckhard Bill; Jeffrey J Urban; R David Britt; Fernande Grandjean; Gary J Long; Serena DeBeer; Frank Neese; Jeffrey A Reimer; Jeffrey R Long

doi:10.1126/science.add7417

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

Science. 2023 Nov 3;382(6670):547-553. doi: 10.1126/science.add7417. Epub 2023 Nov 2.

Authors

Kaipeng Hou^#^{1

2}, Jonas Börgel^#^{1

2}, Henry Z H Jiang¹, Daniel J SantaLucia^{3

4}, Hyunchul Kwon¹, Hao Zhuang^{5

6}, Khetpakorn Chakarawet⁷, Rachel C Rohde¹, Jordan W Taylor¹, Chaochao Dun⁸, Maria V Paley^{1

2}, Ari B Turkiewicz¹, Jesse G Park¹, Haiyan Mao⁵, Ziting Zhu^{2

6}, E Ercan Alp⁹, Jiyong Zhao⁹, Michael Y Hu⁹, Barbara Lavina^{9

10}, Sergey Peredkov³, Xudong Lv¹, Julia Oktawiec¹¹, Katie R Meihaus¹, Dimitrios A Pantazis⁴, Marco Vandone¹², Valentina Colombo^{12

13}, Eckhard Bill³, Jeffrey J Urban^{2

8}, R David Britt^{7

14}, Fernande Grandjean¹⁵, Gary J Long¹⁵, Serena DeBeer³, Frank Neese⁴, Jeffrey A Reimer^{2

5}, Jeffrey R Long^{1

2

5}

Affiliations

¹ Department of Chemistry, University of California, Berkeley, CA 94720, USA.
² Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
³ Max Planck Institute for Chemical Energy Conversion, D-45470 Mülheim an der Ruhr, Germany.
⁴ Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany.
⁵ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720, USA.
⁶ Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA.
⁷ Department of Chemistry, University of California, Davis, CA 95616, USA.
⁸ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
⁹ Advanced Photon Source, Argonne National Laboratory, Lemont, IL 60439, USA.
¹⁰ Center for Advanced Radiation Sources, The University of Chicago, Chicago, IL 60637, USA.
¹¹ Department of Chemistry, Northwestern University, Evanston, IL 60208, USA.
¹² Department of Chemistry, University of Milan, 20133 Milan, Italy.
¹³ Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), UdR Milano, Via Golgi 19, 20133 Milano, Italy.
¹⁴ Miller Institute for Basic Research in Science, University of California, Berkeley CA 94720, USA.
¹⁵ Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO 65409, USA.

^# Contributed equally.

PMID: 37917685
DOI: 10.1126/science.add7417

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 α-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 Kβ 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.