C-H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex

Abstract

The robust, high-valent Ni^IV complex [(Py)₂ Ni^IV 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 Ni^III 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 Ni^IV CF₃ and Ni^III CF₃ centers.

Keywords: fluorine; high-valent species; nickel; reaction mechanisms; trifluoromethylation.