A study was conducted to demonstrate that the poly(picolyl)amine ligand can be transformed into a ligand radical in the coordination sphere of a coordinative unsaturated organometallic IrI(cod) fragment. The N-donor ligands poly(picolyl)amines and a variety of structurally closely related ligands were applied in coordination chemistry and catalysis. It was demonstrated that IrI(cod) complexes with bpa ligands were deprotonated. It was observed that the first and expected deprotonation occurs at the amine donor, followed by a second deprotonation at a neighboring methylene unit. It was also observed that more chemical oxidation by Ag + or O2 leads to a ligand radical complex. The sequence of reactions demonstrated the chemical reactivity of bpa and the redox activity of the deprotonated bpa ligand.