Synthesis of Nickel(I)–Bromide Complexes via Oxidation and Ligand Displacement: Evaluation of Ligand Effects on Speciation and Reactivity

Nickel’s +1 oxidation state has received much interest due to its varied and often enigmatic behavior in increasingly popular catalytic methods. In part, the lack of understanding about NiI results from common synthetic strategies limiting the breadth of complexes that are accessible for mechanistic study and catalyst design. We report an oxidative approach using tribromide salts that allows for the generation of a well-defined precursor, [NiI(COD)Br]2, as well as several new NiI complexes. Included among them are complexes bearing bulky monophosphines, for which structure–speciation relationships are established and catalytic reactivity in a Suzuki–Miyaura coupling (SMC) is investigated. Notably, these routes also allow for the synthesis of well-defined monomeric t-Bubpy-bound NiI complexes, which has not previously been achieved. These complexes, which react with aryl halides, can enable previously challenging mechanistic investigations and present new opportunities for catalysis and synthesis.