Nickel(I) Aryl Species: Synthesis, Properties, and Catalytic Activity.

In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)NiIX (dppf = 1,1'-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)NiI(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-iPr3C6H2). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki-Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki-Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.