Cooperative Ir(III)/Ni(II) Catalysis in a Photoactive Molecular Amine Cage for Visible-Light-Induced Aerobic α-Hydroxylation of β-Keto Esters

Abstract

A photoactive dinuclear Ir(III)-based amine cage was constructed through dynamic imine assembly followed by reductive fixation. Subsequent post-coordination with Ni(II) ions generated a supramolecular catalytic system that integrates visible-light harvesting with Ni(II)-mediated substrate activation, enabling aerobic α-hydroxylation of β-ketoesters under 450 nm irradiation in up to 88% yield.