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C−H Bond Trifluoromethylation of Arenes Enabled by a Robust, High‐Valent Nickel(IV) Complex
Author(s) -
D'Accriscio Florian,
Borja Pilar,
SaffonMerceron Nathalie,
FustierBoutig Marie,
Mézailles Nicolas,
Nebra Noel
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706237
Subject(s) - chemistry , trifluoromethylation , nickel , yield (engineering) , electron paramagnetic resonance , pyridine , nuclear magnetic resonance spectroscopy , monomer , crystallography , spectroscopy , x ray crystallography , stereochemistry , diffraction , medicinal chemistry , materials science , organic chemistry , trifluoromethyl , alkyl , physics , nuclear magnetic resonance , quantum mechanics , metallurgy , polymer , optics
The robust, high‐valent Ni IV complex [(Py) 2 Ni IV F 2 (CF 3 ) 2 ] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X‐ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric Ni III CF 3 complexes 2 ⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X‐ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C−H bond‐breaking/C−CF 3 bond‐forming sequence can occur both at Ni IV CF 3 and Ni III CF 3 centers.