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 κ(3)-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.