The activation of C–F bonds has long been regarded as the subject of research in organometallic chemistry, given their synthetic relevance and the fact that fluorine is the most abundant halogen in the Earth’s crust. However, C–F bond activation remains a largely unsolved challenge due to the high bond dissociation energies, which was historically dominated by transition metal complexes. Main group elements that can cleave unactivated monofluorobenzene are still quite rare and restricted to s-block complexes with a biphilic nature.

The Ni-catalyzed Kumada–Tamao–Corriu (KTC) cross-coupling between aryl fluorides and alkyl Grignard reagents has been used to achieve a highly selective Csp2–Csp3 bond construction via the carbon–fluorine (C–F) bond activation. However, the detailed mechanism of this groundbreaking KTC reaction remains unclear. Herein, we perform a series of analyses by density functional theory (DFT) calculations in order to understand the reaction mechanisms for the selective activation of a highly inert C–F bond by Ni catalysts with bidentate phosphorus ligands.

Fluorine is the most electronegative element in the periodic table. Thus, activation of the carbon–fluorine (C−F) bond, the strongest single bond to carbon, has attracted considerable interest from both experimentalists and theoreticians. In comparison with numerous approaches to activate C−F bonds, the aromaticity‐promoted method is less developed. Herein, we demonstrate that the C−F bond activation could be achieved by a facile tautomerization, benefitting from aromaticity, which can stabilize both the transition states and products.