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This article discusses C-H functionalization reactivity of a Nickel-Imide.
Physical Description
8 p.
Notes
Reprinted with permission from the Journal of the American Chemical Society. Copyright 2012 American Chemical Society.
Abstract: We report report bifunctional reactivity of the β-diketiminato Ni(III)-imide [Me₃NN]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 [Me₃NN]Ni-NHAd (2) for the resulting hydrocarbyl radical R• to give the nickel-amide [Me₃NN]Ni-N(CHMePh)Ad (3) (R-H = ethylbenzene) or aminoalkyl tautomer [Me₃NN]Ni(ɳ²-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 {[Me₃NN]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.
Publication Title:
Journal of the American Chemical Society
Volume:
134
Issue:
24
Page Start:
10114
Page End:
10121
Peer Reviewed:
Yes
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Wiese, Stefan; McAfee, Jason L.; Pahls, Dale R.; McMullin, Claire L.; Cundari, Thomas R., 1964- & Warren, Timothy H.C-H Functionalization Reactivity of a Nickel-Imide,
article,
May 22, 2012;
[Washington, D.C.].
(https://digital.library.unt.edu/ark:/67531/metadc107790/:
accessed June 2, 2024),
University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu;
crediting UNT College of Arts and Sciences.
