Rhodium Catalyzed, Carbon–Hydrogen Bond Directed Hydrodefluorination of Fluoroarenes

[Cp*RhCl(μ-Cl)] 2 is reported as a highly efficient and selective precatalyst for the hydrodefluorination of perfluoroarenes using a hydrocarbon-soluble aluminum dihydride as the terminal reductant. Reactions are directed to cleave a C–F bond adjacent to an existing C–H bond with high regioselectivity (98.5–99%). A heterobimetallic complex containing an extremely rare Al–H–Rh functional group has been isolated and shown to be catalytically competent.