학술논문
Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal–organic framework
Document Type
article
Author
Hou, Kaipeng; Börgel, Jonas; Jiang, Henry ZH; 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
Source
Science. 382(6670)
Subject
Language
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.