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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Oxidative Addition of Aryl Halides to a Ni(I)-Bipyridine Complex
Stephen I Ting1,2, Wendy L Williams1,2, Abigail G Doyle1,2
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Abstract:
The oxidative addition of aryl halides to bipyridine- or phenanthroline-ligated nickel(I) is a commonly proposed step in nickel catalysis. However, there is a scarcity of complexes of this type that both are well-defined and undergo oxidative addition with aryl halides, hampering organometallic studies of this process. We report the synthesis of a well-defined Ni(I) complex, [(CO2Etbpy)NiICl]4 (1). Its solution-phase speciation is characterized by a significant population of monomer and a redox equilibrium that can be perturbed by π-acceptors and σ-donors. 1 reacts readily with aryl bromides, and mechanistic studies are consistent with a pathway proceeding through an initial Ni(I) → Ni(III) oxidative addition to form a Ni(III) aryl species. Such a process was demonstrated stoichiometrically for the first time, affording a structurally characterized Ni(III) aryl complex.
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