Importantly, the presence of iron effectively curtailed this unintended pathway. We hypothesize that this inhibition occurs due to the lower redox potential of Fe(II) compared to chloride (EFeIII/FeII = +0.53 V vs SCE, ECl•/Cl-= +1.12 V vs SCE), essentially making the iron catalyst function as a safeguard against both overoxidation and chlorination of the pyrazole substrates . Meanwhile, the chlorine radical executes C-H bond cleavage adjacent to a heteroatom (i.e., O, N, or S), thus generating a nucleophilic carbon-centered α-oxyalkyl radical (2a˙) . At this point, two scenarios can be envisaged. On the one hand, 2a˙ can be electrochemically oxidized to form a stabilized, electrophilic oxocarbenium ion (2a + ). The latter intermediate is subsequently trapped by the nucleophile, forming the desired C-N bond.