Elucidation of a Redox-Mediated Reaction Cycle for Nickel-Catalyzed Cross Coupling
2018-12-18T00:00:00Z (GMT)
by
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.
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CC BY-NC 4.0