N₂O Activation and Oxidation Reactivity from a Non-Heme Iron Pyrrole Platform

We report the design, syntheses, and oxidation reactivity of a new family of non-heme iron pyrrole complexes. The most reactive congener is capable of activating N₂O, an appealing yet challenging oxidant, for oxygen atom transfer. The first generation tpa^PhFe complex reacts with oxygen atom donors to generate a ligand hydroxylated species by intramolecular C−H activation and oxygenation. The second-generation tpa^MesFe system expands on this reactivity to intermolecular hydrogen atom abstraction chemistry through N₂O activation. The observation of arene C−H hydroxylation and the consumption of external hydrogen atom donors implicates a potent metal-centered oxidant, likely an iron(IV)-oxo species, along these reaction pathways. This work establishes a new coordination platform for high-valent iron reactivity.