Communication
A Two-Coordinate Nickel Imido Complex That Effects C−H Amination
Abstract
An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N2 from a bulky aryl azide in its reaction with (IPr*)Ni(η6-C7H8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ2-N(dmp)CH2CH2} (4).
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This article has been cited by 1 ACS Journal articles (1 most recent appear below).
Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron(III) Complex
Ryan E. Cowley, Nathan A. Eckert, Sridhar Vaddadi, Travis M. Figg, Thomas R. Cundari, and Patrick L. HollandJournal of the American Chemical Society2011 133 (25), 9796-9811Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron(III) Complex
Ryan E. Cowley, Nathan A. Eckert, Sridhar Vaddadi, Travis M. Figg, Thomas R. Cundari, and Patrick L. HollandJournal of the American Chemical Society2011 133 (25), 9796-9811In the literature, iron–oxo complexes have been isolated and their hydrogen atom transfer (HAT) reactions have been studied in detail. Iron–imido complexes have been isolated more recently, and the community needs experimental evaluations of the mechanism ...
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History
- Published In Issue February 02, 2011
- Article ASAPDecember 22, 2010
- Received: November 10, 2010