Selective Aromatic C–H Hydroxylation Enabled by η6‑Coordination to Iridium(III)

We report an aromatic C–H hydroxylation protocol in which the arene is activated through η6-coordination to an iridium­(III) complex. η6-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate η5-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene π-activation into a catalytic cycle for C–H functionalization.