The novel dinuclear complex related to the [FeFe]-hydrogenases active site, [Fe2(μ-pdt)(κ2-dmpe)2(CO)2] (1), is highly reactive toward chlorinated compounds CHxCl4-x (x = 1, 2) affording selectively terminal or bridging chloro diiron isomers through a C-Cl bond activation. DFT calculations suggest a cooperative mechanism involving a formal concerted regioselective chloronium transfer depending on the unrotated or rotated conformation of two isomers of 1.