C-H Functionalization Reactivity of a Nickel-Imide

Description:

This article discusses C-H functionalization reactivity of a Nickel-Imide.

Creator(s):
Creation Date: May 22, 2012
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Wiese, Stefan

Georgetown University

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McAfee, Jason L.

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Pahls, Dale R.

University of North Texas

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McMullin, Claire L.

University of North Texas

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Cundari, Thomas R., 1964-

University of North Texas

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Warren, Timothy H.

Georgetown University

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: May 22, 2012
Description:

This article discusses C-H functionalization reactivity of a Nickel-Imide.

Degree:
Department: Chemistry
Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2012 American Chemical Society.

Note:

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.

Physical Description:

8 p.

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Subject(s):
Keyword(s): hydrocarbyl radicals | dinickel imide | C-H amination systems
Source: Journal of the American Chemical Society, 2012, Washington DC: American Chemical Society, pp. 10114-10121
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja302149k
  • ARK: ark:/67531/metadc107790
Resource Type: Article
Format: Text
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Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 134
Issue: 24
Page Start: 10114
Page End: 10121
Peer Reviewed: Yes