Amphoteric reactivity of iron(III)–hydroperoxo complex generated from proton- and salicylate-assisted dioxygen activation

We report the synthesis and characterization of an iron(III)–hydroperoxo complex generated from salicylate-assisted dioxygen activation by a cation–liganded iron(II) complex. Spectroscopic and theoretical data revealed stabilization of the end-on hydroperoxo ligand, and mechanistic insights, including a ‘‘V-shaped’’ Hammett plot, were confirmed by conducting oxygen atom transfer and proton-coupled electron transfer reactions.