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Updated: Feb 24, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
C-H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex
Florian D'Accriscio1, Pilar Borja1, Nathalie Saffon-Merceron2
1Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier, CNRS, 118 Route de Narbonne, 31062, Toulouse, France.
Abstract:
The robust, high-valent NiIV complex [(Py)2 NiIV F2 (CF3 )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 NiIII CF3 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-CF3 bond-forming sequence can occur both at NiIV CF3 and NiIII CF3 centers.
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