Catalytic Hydrogenolysis of Aryl C–F Bonds Using a Bimetallic Rhodium–Indium Complex

A homogeneous rhodium–indium catalyst hydrodefluorinates substrates bearing strong aryl C–F bonds, including difluoro- and fluorobenzene, using 1 atm of H2, alkoxide bases, and moderate temperatures (70–90 °C). Characterization of catalytic intermediates establishes a formal Rh–I/RhI redox cycle. The Rh → In interaction is proposed to enable catalysis by stabilizing the reactive Rh–I species, which is responsible for cleaving the Ar–F bond and is ultimately regenerated using H2 and base.