The preparation of three families of phosphorescent iridium(III) emitters, including iridaoxazole derivatives, hydroxycarbene compounds, and N,C(sp3),C(sp2),O-tetradentate containing complexes, has been performed starting from dimers cis-[Ir(μ2-η2-C≡CR){κ2-C,N-(MeC6H3-py)}2]2 (R = tBu (1a), Ph (1b)). Reactions of 1a with benzamide, acetamide, phenylacetamide, and trifluoroacetamide lead to the iridaoxazole derivatives Ir{κ2-C,O-[C(CH2tBu)NC(R)O]}{κ2-C,N-(MeC6H3-py)}2 (R = Ph (2), Me (3), CH2Ph (4), CF3 (5)) with a fac disposition of carbons and heteroatoms around the metal center. In 2-methyltetrahydrofuran and dichloromethane, water promotes the C-N rupture of the IrC-N bond of the iridaoxazole ring of 3-5 to form amidate-iridium(III)-hydroxycarbene derivatives Ir{κ1-N-[NHC(R)O]}{κ2-C,N-(MeC6H3-py)}2{═C(CH2tBu)OH} (R = Me (6), CH2Ph (7), CF3 (8)). In contrast to 1a, dimer 1b reacts with benzamide and acetamide to give Ir{κ4-N,C,C',O-[py-MeC6H3-C(CH2-C6H4)NHC(R)O]}{κ2-C,N-(MeC6H3-py)}(R = Ph (9), Me (10)), which bear a N,C(sp3),C(sp2),O-tetradentate ligand resulting from a triple coupling (an alkynyl ligand, an amide, and a coordinated aryl group) and a C-H bond activation at the metal coordination sphere. Complexes 2-4 and 6-10 are emissive upon photoexcitation, in orange (2-4), green (6-8), and yellow (9 and 10) regions, with quantum yields between low and moderate (0.01-0.50) and short lifetimes (0.2-9.0 μs).