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Table of Contents

Communication

A Two-Coordinate Nickel Imido Complex That Effects C−H Amination

Carl A. Laskowski†, Alexander J. M. Miller‡, Gregory L. Hillhouse*†, and Thomas R. Cundari*§

^† Gordon Center for Integrative Science, Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States

^‡ Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, United States

^§ Center for Advanced Scientific Computing and Modeling, Department of Chemistry, University of North Texas, Denton, Texas 76203, United States

J. Am. Chem. Soc., 2011, 133 (4), pp 771–773

DOI: 10.1021/ja1101213

Publication Date (Web): December 22, 2010

g-hillhouse@uchicago.edu; t@unt.edu

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. Holland
Journal of the American Chemical Society2011 133 (25), 9796-9811
- 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. Holland
  Journal of the American Chemical Society2011 133 (25), 9796-9811
  In 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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