The Odd Couple: Oxidative Coupling of an Iridium(III) Phenylimido Complex

Catalytic arylnitrene transfer often results in catalyst decay via aromatic coupling reactions. We here report a case study for the oxidative coupling of an in situ formed iridium(III) phenyimido complex with a triplet ground state. The nitrenoid species is inherently unstable towards oxidative coupling in para ‐position to give a dinuclear, diphenoquinone‐diiminato bridged Ir II /Ir II complex. Thermochemical, kinetic, and computational examinations show that the CC coupling is driven by abstraction of the weak CH bonds.