Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable P III Lewis Acid

Catalytic hydrodefluorination (HDF) of unactivated fluoroalkanes or CF 3 ‐substituted aryl species is performed using the P III Lewis acids, [(bipy)PPh] 2+ ( 1 2+ ) and [(terpy)PPh] 2+ ( 2 2+ ) under mild conditions (25 or 50 °C). Mechanistic studies indicate that activation of C−F bond by the P III center is key. Particularly noteworthy is that the catalyst 2 [B(C 6 F 5 ) 4 ] 2 is air‐stable and readily accessible from bench‐stable, commercially available reagents in one‐step and can be used without isolation.