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

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 PeredkovXudong 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

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English (US)
Pages (from-to)	547-553
Number of pages	7
Journal	Science
Volume	382
Issue number	6670
DOIs	https://doi.org/10.1126/science.add7417
State	Published - Nov 1 2023

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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., ... Long, J. R. (2023). Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework. Science, 382(6670), 547-553. https://doi.org/10.1126/science.add7417

Hou, K, Börgel, J, Jiang, HZH, SantaLucia, DJ, Kwon, H, Zhuang, H, Chakarawet, K, Rohde, RC, Taylor, JW, Dun, C, Paley, MV, Turkiewicz, AB, Park, JG, Mao, H, Zhu, Z, Ercan Alp, E, Zhao, J, Hu, MY, Lavina, B, Peredkov, S, Lv, X, Oktawiec, J, Meihaus, KR, Pantazis, DA, Vandone, M, Colombo, V, Bill, E, Urban, JJ, David Britt, R, Grandjean, F, Long, GJ, DeBeer, S, Neese, F, Reimer, JA & Long, JR 2023, 'Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework', Science, vol. 382, no. 6670, pp. 547-553. https://doi.org/10.1126/science.add7417

@article{b528b621d2c543079904e7989ec874be,

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

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 M{\"o}ssbauer, 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.",

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

year = "2023",

month = nov,

day = "1",

doi = "10.1126/science.add7417",

language = "English (US)",

volume = "382",

pages = "547--553",

journal = "Science",

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publisher = "American Association for the Advancement of Science",

number = "6670",

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T1 - Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework

AU - Hou, Kaipeng

AU - Börgel, Jonas

AU - Jiang, Henry Z.H.

AU - SantaLucia, Daniel J.

AU - Kwon, Hyunchul

AU - Zhuang, Hao

AU - Chakarawet, Khetpakorn

AU - Rohde, Rachel C.

AU - Taylor, Jordan W.

AU - Dun, Chaochao

AU - Paley, Maria V.

AU - Turkiewicz, Ari B.

AU - Park, Jesse G.

AU - Mao, Haiyan

AU - Zhu, Ziting

AU - Ercan Alp, E.

AU - Zhao, Jiyong

AU - Hu, Michael Y.

AU - Lavina, Barbara

AU - Peredkov, Sergey

AU - Lv, Xudong

AU - Oktawiec, Julia

AU - Meihaus, Katie R.

AU - Pantazis, Dimitrios A.

AU - Vandone, Marco

AU - Colombo, Valentina

AU - Bill, Eckhard

AU - Urban, Jeffrey J.

AU - David Britt, R.

AU - Grandjean, Fernande

AU - Long, Gary J.

AU - DeBeer, Serena

AU - Neese, Frank

AU - Reimer, Jeffrey A.

AU - Long, Jeffrey R.

PY - 2023/11/1

Y1 - 2023/11/1

N2 - 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.

AB - 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.

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VL - 382

SP - 547

EP - 553

JO - Science

JF - Science

IS - 6670

ER -

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

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