To explore the catalytic potential of Ir II complexes compared to isostructural Ir I analogues, we have synthesized a small family of mononuclear Ir II metalloradicals bearing a pincer POCOP ligand (POCOP = C6H3-2,6-(OP( t Bu)2)2). We already demonstrated that oxidation of the Ir I precursor [Ir(POCOP)N2] (1) with AgOTf or Ag[BAr F ] leads to the corresponding Ir II compounds, Ir(POCOP)OTf and [Ir(POCOP)N2][BAr F ] (1•BAr F ), respectively (Scheme 1; OTf -= trifluoromethanesulfonate, [BAr F ] -= tetrakis phenyl]borate). While the triflate anion replaces the dinitrogen ligand to access an overall neutral structure, the even lower coordinating capacity of the [BAr F ] -anion results in an ionic pair with the dinitrogen molecule retained. Anticipating that the coordinating capacity of the anion may have an impact on catalysis, we have now considered alternative silver salts with various anions and performed the oxidation of Ir I not only from the dinitrogen precursor 1, but also from its related ethylene analogue [Ir(POCOP)(C2H4)] ( ).