C-H functionalization reactivity of a nickel-imide

Stefan Wiese, Jason L. McAfee, Dale R. Pahls, Claire L. McMullin, Thomas R. Cundari, Timothy H. Warren

Research output: Contribution to journalArticlepeer-review

104 Scopus citations

Abstract

We report bifunctional reactivity of the β-diketiminato Ni(III)-imide [Me 3NN]Ni=NAd (1), which undergoes H-atom abstraction (HAA) reactions with benzylic substrates R-H (indane, ethylbenzene, toluene). Nickel-imide 1 competes with the nickel-amide HAA product [Me 3NN]Ni-NHAd (2) for the resulting hydrocarbyl radical R to give the nickel-amide [Me 3NN]Ni-N(CHMePh)Ad (3) (R-H = ethylbenzene) or aminoalkyl tautomer [Me 3NN]Ni(η 2-CH(Ph)NHAd) (4) (R-H = toluene). A significant amount of functionalized amine R-NHAd is observed in the reaction of 1 with indane along with the dinickel imide {[Me 3NN]Ni} 2(μ-NAd) (5). Kinetic and DFT analyses point to rate-limiting HAA from R-H by 1 to give R , which may add to either imide 1 or amide 2, each featuring significant N-based radical character. Thus, these studies illustrate a fundamental competition possible in C-H amination systems that proceed via a HAA/radical rebound mechanism.

Original languageEnglish (US)
Pages (from-to)10114-10121
Number of pages8
JournalJournal of the American Chemical Society
Volume134
Issue number24
DOIs
StatePublished - Jun 20 2012

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