Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0).

ABSTRACT: The mechanism of the reactions between dppf-Ni⁰ complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ²-dppf)(κ¹-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand.

SUBMITTER: Greaves ME 

PROVIDER: S-EPMC7507766 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature