ja8b11262_si_002.cif (2.97 MB)
Elucidation of a Redox-Mediated Reaction Cycle for Nickel-Catalyzed Cross Coupling
dataset
posted on 2018-12-18, 00:00 authored by Rui Sun, Yangzhong Qin, Serge Ruccolo, Christoph Schnedermann, Cyrille Costentin, Daniel G. NoceraA 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.