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

• 成果类型: Article
• 署名作者: Hou, Kaipeng; Borgel, 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.
• 署名单位: University of California System; University of California Berkeley; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; Max Planck Society; Max Planck Society; University of California System; University of California Berkeley; University of California System; University of California Berkeley; University of California System; University of California Davis; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; United States Department of Energy (DOE); Argonne National Laboratory; University of Chicago; Northwestern University; University of Milan; University of California System; University of California Berkeley; University of Missouri System; Missouri University of Science & Technology; Mahidol University; Korea Advanced Institute of Science & Technology (KAIST)
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10028
• DOI: 10.1126/science.add7417
• 发表日期: 2023-11-03
• 页码: 547-553
• 关键词: alpha-ketoglutarate dioxygenase; oxygen activation; oxoiron(iv) complex; active-site; nonheme; oxidation; methane; ethane; o-2; intermediate

摘要

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 alpha-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 Mossbauer, Fe K beta 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.