Catalytic C–F Bond Hydrogenolysis of Fluoroaromatics by [(η⁵‑C₅Me₅)Rh^I(2,2′-bipyridine)]

A new class of efficient catalyst, the Rh­(I) complex [(η5-C5Me5)­RhI(bpy)] (1; bpy = 2,2′-bipyridine), for the C–F bond hydrogenolysis of fluoroaromatics (C6F5CF3, C6F6, C6F5H, and C6F5CH3) is presented. The best turnover number of 380 for C6F6 is afforded by using 0.1 mol % of 1, 0.8 MPa of H2, and 2 equiv of Et2NH in CH3CN at 25 °C. The successful isolation of the C–F bond cleavage product [(η5-C5Me5)­RhIII(bpy)­(C6F5)]­(F) as a plausible intermediate of the catalytic hydrogenolysis of C6F6 by 1 is also described.