The effect of added ligands on the reactions of [Ni(COD)(dppf)] with alkyl halides: halide abstraction may be reversible

Megan E. Greaves, Thomas O. Ronson, Feliu Maseras, David J. Nelson

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The reactions of dppf-nickel(0) with alkyl halides proceed via three-coordinate nickel(0) intermediates of the form [Ni(dppf)(L)]. The effects of the identity of the added ligand (L) on catalyst speciation and the rates of reactions of [Ni(COD)(dppf)] with alkyl halides have been investigated using kinetic experiments and density functional theory calculations. A series of monodentate ligands have been investigated in attempts to identify trends in reactivity. Sterically bulky and electron-donating ligands are found to decrease the reaction rate. It was found that (i) the halide abstraction step is not always irreversible and the subsequent recombination of a nickel(I) complex with an alkyl halide can have a significant effect on the overall rate of the reaction and (ii) some ligands lead to very stable [Ni(dppf)(L) 2] species. The yields of prototypical (dppf)nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are significantly improved by the addition of free ligands, which provides another important variable to consider when optimizing nickel-catalyzed reactions of alkyl halides.

Original languageEnglish
Pages (from-to)1997-2007
Number of pages11
Issue number12
Publication statusPublished - 16 Jun 2021


  • nickel
  • homogeneous catalysis
  • cross-coupling
  • reaction mechanisms
  • organometallic chemistry

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