The novel dinuclear complex related to the [FeFe]-hydrogenases active site, [Fe$_2$(μ-pdt)(${κ^2}$-dmpe)$_2$(CO)$_2$] (1), is highly reactive toward chlorinated compounds CH$_x$Cl$_{4–x}$ (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.