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

Samuel H Newman-Stonebraker; T Judah Raab; Hootan Roshandel; Abigail G Doyle

doi:10.1021/jacs.3c06233

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

J Am Chem Soc. 2023 Sep 6;145(35):19368-19377. doi: 10.1021/jacs.3c06233. Epub 2023 Aug 23.

Authors

Samuel H Newman-Stonebraker^{1

2}, T Judah Raab², Hootan Roshandel², Abigail G Doyle²

Affiliations

¹ Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
² Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, California 90095, United States.

Abstract

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 Ni^I 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, [Ni^I(COD)Br]₂, as well as several new Ni^I 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 Ni^I 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.

Abstract

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