Photoinduced Group Transposition via Iridium‐Nitrenoid Leading to Amidative Inner‐Sphere Aryl Migration

Abstract

AbstractWe herein report a fundamental mechanistic investigation into photochemical metal‐nitrenoid generation and inner‐sphere transposition reactivity using organometallic photoprecursors. By designing Cp*Ir(hydroxamate)(Ar) complexes, we induced photo‐initiated ligand activation, allowing us to explore the amidative σ(Ir–aryl) migration reactivity. A combination of experimental mechanistic studies, femtosecond transient absorption spectroscopy, and density functional theory (DFT) calculations revealed that the metal‐to‐ligand charge transfer enables the σ(N−O) cleavage, followed by Ir‐acylnitrenoid generation. The final inner‐sphere σ(Ir–aryl) group migration results in a net amidative group transposition.