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

In nature, nonheme iron-containing enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although scientists have long sought to mimic this reactivity, the enzyme-like activation of dioxygen to form high-spin iron(IV)=O species remains an unrealized goal in synthetic chemistry. 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 dioxygen 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 dioxygen, the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.