title: Carbon-carbon cross-coupling reactions catalyzed by a two-coordinate nickel(II)-bis(amido) complex via observable Ni(I) , Ni(II) , and Ni(III) intermediates.
abstract: Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for cross-coupling reactions has attracted significant interest. One of the key intermediates invoked in these reactions is a Ni(III) -alkyl species, but no such species that is part of a competent catalytic cycle has yet been isolated. Herein, we report a carbon-carbon cross-coupling system based on a two-coordinate Ni(II) -bis(amido) complex in which a Ni(III) -alkyl species can be isolated and fully characterized. This study details compelling experimental evidence of the role played by this Ni(III) -alkyl species as well as those of other key Ni(I) and Ni(II) intermediates. The catalytic cycle described herein is also one of the first examples of a two-coordinate complex that competently catalyzes an organic transformation, potentially leading to a new class of catalysts based on the unique ability of first-row transition metals to accommodate two-coordinate complexes.
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720 (USA).
authors.forename: Michael I
authors.initials: MI
authors.lastname: Lipschutz
authors.forename: T Don
authors.initials: TD
authors.lastname: Tilley
keywords: cross-coupling; homogeneous catalysis; mechanism; metal amides; nickel