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

Abstract

Abstract 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.