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 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.