Hydrocarbon oxidation reactivity in iron metal-organic frameworks

High-valent iron-oxo intermediates are implicated in a variety of oxidative enzymes, many of which are capable of the selective partial oxidn. of strong aliph. and arom. C-H bonds. However, mol. iron-oxo species often lack stability, decaying via pathways such as dimerization and self-oxidn., while heterogeneous analogs are often difficult to characterize and modify. These challenges may be mitigated in metal-org. frameworks featuring well-defined and site-isolated iron centers. Herein, we report the hydrocarbon oxidn. activity of a variety of iron metal-org. frameworks, including Fe2(dobdc) and its magnesium-dild. analogs, using nitrous oxide as the terminal oxidant. Although the intermediate has not been isolated, reactivity studies along with detailed characterization of decay products indicate that the active oxidant is likely an iron(IV)-oxo species.