The reaction of a terminal alkyne (RCCH) and 2-aminopyridine (R′C5NH3NH2) with the dinuclear species [Cp*IrCl2]2 afforded the cationic aminocarbene derivatives Cp*Ir(Cl)[ =C(CH2R)NHC5NH 3R′] via a hydroamination and a ligand substitution. The reaction pathway has been examined through computational studies. © 2013 American Chemical Society.