Meucci, Elizabeth A.Nguyen, Shay N.Camasso, Nicole M.Chong, EugeneAriafard, AlirezaCanty, Allan J.Sanford, Melanie S.2025-12-162025-12-160002-7863PubMed:31379153ORCID:/0000-0003-2383-6380/work/197987412https://hdl.handle.net/1885/733795598This Article describes the development of a stable NiIV complex that mediates C(sp2)-H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a NiIV-catalyzed C-H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanistic studies support a radical chain pathway involving NiIV, NiIII, and NiII intermediates.This work was supported by the National Science Foundation (NSF) Grant CHE-1111563, the Australian Research Council, and the Australian National Computing Infrastructure. We also thank Rackham Graduate School and the NSF for graduate fellowships to E.A.M., the NSF for a REU summer fellowship for S.N.N., and the NSERC for a postdoctoral fellowship for E.C. We gratefully acknowledge Dr. Jeff Kampf for X-ray crystallographic analysis of complex II , as well as funding from NSF Grant CHE-0840456 for X-ray instrumentation.8en© 2019 The Authors2019-08-1410.1021/jacs.9b0638385071002612