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

Journal Article · · Science
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  1. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. University of California, Berkeley, CA (United States)
  3. Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany);Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr (Germany)
  4. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
  5. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division; University of California, Berkeley, CA (United States)
  6. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  7. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); University of Chicago, IL (United States)
  8. Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
  9. Northwestern University, Evanston, IL (United States)
  10. University of California, Berkeley, CA (United States);
  11. Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr (Germany)
  12. University of Milan (Italy)
  13. University of Milan (Italy); Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Milano (Italy)
  14. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
  15. University of California, Davis, CA (United States); University of California, Berkeley, CA (United States)
  16. Missouri University of Science and Technology, Rolla, MO (United States)
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Institutes of Health (NIH); National Institute of General Medical Sciences; Italian Ministry of University and Research
Grant/Contract Number:
AC02-05CH11231; SC0019992; AC02-06CH11357; S10OD024998; 1R35GM126961; S10OD023532; F32GM143925
OSTI ID:
2229281
Journal Information:
Science, Vol. 382, Issue 6670; ISSN 0036-8075
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

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