N2O activation and oxidation reactivity from a non-heme iron pyrrold 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(Ph)Fe complex reacts with oxygen atom donors to generate a ligand hydroxylated species by intramolecular C-H activation and oxygenation. The second-generation tpa(Mes)Fe 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.