Bimetallic Metal–Organic Coordination Polymers Facilitated the Selective C–F Cleavage of Polyfluoroarenes

Selective C–F bond cleavage of polyfluoroarenes has attracted tremendous interest due to its promising applications in introducing fluorinated building blocks into organic molecules. However, it remains a challenge to achieve highly site-selective C–F bond cleavage because of the intrinsic inertness of the C–F bond and the difficulty in distinguishing specific C–F bonds on the aromatic ring. Herein we report an efficient nucleophilic aromatic substitution (SNAr) reaction of polyfluoroarenes with Grignard reagents that employs MnFe-based bimetallic metal–organic coordination polymers (MOCPs) as recyclable and reusable heterogeneous catalysts. Significantly, in this reaction, the prepared MOCP (Mn–Fe) catalyst exhibited excellent activity in selective C–F bond cleavage and afforded a series of functionalized polyfluoroarenes in moderate to excellent yields (up to 96%). This work highlights the potential of MOCP catalysts to serve as a tunable platform in Lewis acid catalysis.