In summary, through spectroscopic and electrochemical studies, this work provides mechanistic insights into an oxidative quenching pathway in dual Ni/PC catalyzed C-X bond forming reactions. Specifically, oxidative quenching of the PC excited state to form a Ni(I) complex was observed spectroscopically, as well as the subsequent oxidative addition of an aryl iodide at Ni(I) and consequent oxidation of iodide by Ir(IV). Interestingly, persistent tight ion pairing in a series of [Ir][Ni] complexes was invoked to simulate the observed oxidative addition kinetics. Future studies ought to confirm or falsify this deduction by utilizing experimental methods capable of distinguishing tight and solvent separated ion pairs formed as a result of PET, such as time resolved dielectric loss spectroscopy. Additionally, turnover of the Ir(IV) species to recover Ir(III) by halides (Br-, I-) or Ni(I) was confirmed with spectroelectrochemistry and ns-TA experiments. A new role of chloride additive was discovered in binding to the Ni center to displace DBU, forming an octahedral Ni chloride species which led to a significant increase in reactivity to enable coupling of electron deficient/neutral aryl chlorides and highly electron rich aryl bromides. Notably, a novel loratadine derivative was synthesized with the reoptimized conditions, supporting the potential utility of the method discovered through the mechanistic studies herein for late-stage functionalization of medicinally relevant compounds.