Tactics for uncovering intermediates in nickel Kumada cross-coupling catalysis

In this issue of Chem, L.M. Mirica and co-workers elucidate the roles of NiI and NiIII intermediates in the Kumada cross-coupling reaction by using the tridentate ligand iPr3TACN. Their research highlights the stabilization of these intermediates by acetonitrile and the resulting enhanced catalytic efficiency and provides insights into ligand design. In this issue of Chem, L.M. Mirica and co-workers elucidate the roles of NiI and NiIII intermediates in the Kumada cross-coupling reaction by using the tridentate ligand iPr3TACN. Their research highlights the stabilization of these intermediates by acetonitrile and the resulting enhanced catalytic efficiency and provides insights into ligand design. A bulky 1,4,7-triazacyclononane and acetonitrile, a Goldilocks system for probing the role of NiIII and NiI centers in cross-coupling catalysisGriego et al.ChemDecember 14, 2023In BriefIn nickel-catalyzed alkyl-alkyl cross-coupling reactions, paramagnetic Ni(I) and Ni(III) species are proposed to be the active intermediates. This study provides unambiguous evidence for the involvement of both Ni(III) and Ni(I) organometallic species in such cross-coupling reactions. In addition, the presence of acetonitrile or other alkyl nitriles improves the product yield in a multifaceted fashion, suggesting that the presence of a coordinating solvent and a weak π-acceptor, such as acetonitrile, could have a beneficial effect for a range of Ni-mediated organometallic transformations. Full-Text PDF