“…The activation of C–Cl bonds by transition metal complexes represents a crucial objective motivated by economic and environmental imperatives, whether for employing chlorocarbons as substrates or facilitating dechlorination processes. − While numerous mononuclear complexes able to activate small CH x Cl 4– x ( x = 1, 2) substrates have been reported, − well-defined polymetallic complexes (generally based on second to third row transition metals), which induce the cleavage of C–Cl bonds of polychlorinated molecules, are more scarce. − Despite the existence of numerous diiron complexes inspired by the [FeFe]-hydrogenase metal cofactor, their activity, other than that concerning the H + /H 2 conversion, − has been little explored. − The activation of chlorinated organic molecules with such Fe 2 complexes has never been reported. Here, we present the reactivity toward polychlorinated molecules of the bis-chelated complex [Fe 2 (μ-pdt)(κ 2 -dmpe) 2 (CO) 2 ] ( 1 ) (dmpe: 1,2-bis(dimethylphosphino)ethane; pdt: propanedithiolate), a new example of tetrasubstituted diiron dithiolate complex. − The cleavage of C–Cl bonds through an unusual cooperative bimetallic mechanism, involving formal regioselective chloronium transfer, has been investigated by DFT.…”