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

The robust, high‐valent Ni^IV complex [(Py)₂Ni^IVF₂(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^IIICF₃ 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^IVCF₃ and Ni^IIICF₃ centers.