1. Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal-organic framework.
- Author
-
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, Alp EE, Zhao J, Hu MY, Lavina B, Peredkov S, Lv X, Oktawiec J, Meihaus KR, Pantazis DA, Vandone M, Colombo V, Bill E, Urban JJ, Britt RD, Grandjean F, Long GJ, DeBeer S, Neese F, Reimer JA, and Long JR
- 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 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 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.- Published
- 2023
- Full Text
- View/download PDF