C–Cl Bond Activation at Rotated vs Unrotated Dinuclear Site Related to [FeFe]-Hydrogenases

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 CH_xCl_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.