Aryl–Fluoride Bond-Forming Reductive Elimination from Nickel(IV) Centers

The treatment of pyridine- and pyrazole-ligated Ni^II σ-aryl complexes with Selectfluor results in C(sp²)–F bond formation under mild conditions. With appropriate design of supporting ligands, diamagnetic Ni^IV σ-aryl fluoride intermediates can be detected spectroscopically and/or isolated during these transformations. These studies demonstrate for the first time that Ni^IV σ-aryl fluoride complexes participate in challenging C(sp²)–F bond-forming reductive elimination to yield aryl fluoride products.