LAUSR

A reaction cycle for redox-mediated, Ni-catalyzed aryl etherification is proposed under both photoredox and electrochemically mediated conditions. We demonstrate that a self-sustained Ni(I/III) cycle is operative in both cases by chemically synthesizing and characterizing a common paramagnetic Ni intermediate and establishing its catalytic activity. Furthermore, deleterious pathways leading to off-cycle Ni(II) species have been identified, allowing us to discover optimized conditions for achieving self-sustained reactivity at a ∼15-fold increase in the quantum yield and a ∼3-fold increase in the faradaic yield. These results highlight the importance of leveraging insight of complete reaction cycles for increasing the efficiency of redox-mediated reactions.