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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
Author(s) -
Lipschutz Michael I.,
Tilley T. Don
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201404577
Subject(s) - nickel , catalysis , catalytic cycle , alkyl , chemistry , carbon fibers , transition metal , coupling reaction , stereochemistry , organic chemistry , materials science , composite number , composite material
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.