Rare Earth Metal Catalyzed C–F Bond Activation

Cp3Ln (Ln = Ce, Nd, Sm, Er, Yb) are applied as precatalysts in the presence of LiAlH4 for the C–F bond activation of hexafluoropropene, 1,1,3,3,3‐pentafluoropropene, trifluoropropene, chlorotrifluoroethene, and octafluorotoluene. 100 % conversion and TONs up to 155 could be observed for the hydrodefluorination reaction (HDF). For chlorotrifluoroethene hydrodefluorination occurs with high chemoselectivity favoring the C–F bond activation versus C–Cl bond activation.