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Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation
Author(s) -
Dürr Alexander B.,
Fisher Henry C.,
Kalvet Indrek,
Truong KhaiNghi,
Schoenebeck Franziska
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706423
Subject(s) - reactivity (psychology) , nickel , catalysis , dimer , chemistry , aryl , chemoselectivity , coupling reaction , coupling (piping) , combinatorial chemistry , materials science , organic chemistry , medicine , alternative medicine , alkyl , metallurgy , pathology
We herein showcase the ability of NHC‐coordinated dinuclear Ni I –Ni I complexes to override fundamental reactivity limits of mononuclear (NHC)Ni 0 catalysts in cross‐couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a Ni I dimer. A novel SeCF 3 ‐bridged Ni I dimer was isolated and shown to selectively react with Ar−I bonds. Our computational and experimental reactivity data suggest dinuclear Ni I catalysis to be operative. The corresponding Ni 0 species, on the other hand, suffers from preferred reaction with the product, ArSeCF 3 , over productive cross‐coupling and is hence inactive.