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Nickel(II/IV) manifold enables room-temperature C(sp3)H functionalization


Roberts, CC and Chong, E and Kampf, JW and Canty, AJ and Ariafard, A and Sanford, MS, Nickel(II/IV) manifold enables room-temperature C(sp3)-H functionalization, Journal of the American Chemical Society, 141, (49) pp. 19513-19520. ISSN 0002-7863 (2019) [Refereed Article]

Copyright Statement

2019 American Chemical Society

DOI: doi:10.1021/jacs.9b11999


This article demonstrates a mild oxidatively induced C(sp3)H activation at a high-valent Ni center. In contrast with most C(sp3)H activation reactions at NiII, the transformation proceeds at room temperature and generates an isolable NiIV σ-alkyl complex. Density functional theory studies show two plausible mechanisms for this CH activation process involving triflate-assisted CH cleavage at either a NiIV or a NiIII intermediate. The former pathway is modestly favored over the latter (by ∼3 kcal/mol). The NiIV σ-alkyl product of CH cleavage reacts with a variety of nucleophiles to form C(sp3)X bonds (X = halide, oxygen, nitrogen, sulfur, or carbon). These stoichiometric transformations can be coupled using N-fluoro-2,4,6-trimethylpyridinium triflate as a terminal oxidant in conjunction with chloride as a nucleophile to achieve a proof-of-principle NiII/IV-catalyzed C(sp3)H functionalization reaction.

Item Details

Item Type:Refereed Article
Keywords:organonickel, C-H activation, nickel(IV), DFT, organometallic mechanism
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:136342
Year Published:2019
Web of Science® Times Cited:11
Deposited By:Chemistry
Deposited On:2019-12-16
Last Modified:2020-02-28

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