Iridium Complexes of the Doubly Cyclometalated NHC Ligand IMes′′

Two consecutive C–H bond activations at the coordination sphere of Ir transform the commonly employed NHC ligand IMes into the new κ3-C fac-coordinating ligand IMes′′. The preparation and structure of Ir(III) complexes featuring this ligand together with selected reactions toward small molecules that illustrate their reactivity keys are described.