Utilising Sodium‐Mediated Ferration for Regioselective Functionalisation of Fluoroarenes via C−H and C−F Bond Activations

Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5⋅NaFe(HMDS)3] (1) enables regioselective mono and di‐ferration (via direct Fe−H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore, using excess 1 at 80 °C switches on a remarkable cascade process inducing the collective twofold C−H/threefold C−F bond activations, where each C−H bond is transformed to a C−Fe bond whereas each C−F bond is transformed into a C−N bond. Zwei Metalle kooperieren im Natriumtri(amido)ferrat 1 bei der kollektiven Spaltung von fünf Bindungen über eine Aktivierungskaskade. Drei C‐F‐ und zwei C‐H‐Bindungen in Trifluorarenen werden gespalten.