Nitrene transfer to an iridium(Cp*) complex with a pyridyl-amide bidentate ligand drives an unexpected outer-sphere C鈥揌 activation and amide functionalization reaction mediated by this metal center. This is a significant departure from C鈥揘 bond-forming processes in mononuclear rhodium and iridium catalysts, which require C鈥揌 activation at the metal center prior to nitrene transfer and insertion (an inner-sphere C鈥揌 insertion pathway). The mechanism likely involves a high oxidation state iridium-imido reactive species capable of hydrogen atom abstraction and a radical-based rearrangement during the formation of the ultimate iridium product.