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The reaction of the PPN+ salt of [Fe4C(CO)12]2- with ClHgM (M = metal fragment) in CH2Cl2 gives the new hexanuclear carbide clusters (PPN)[Fe4C(CO)12{μ-HgM}] (M = Mo(CO)3Cp (1), W(CO)3Cp (2), Mn(CO)5 (3), Fe(CO)2Cp (4), Co(CO)4 (5)) in good yields. The X-ray crystal structure of 1 is without precedent in that a mercury atom bridges one of the two edges defined by wingtip and hinge iron atoms of the Fe4C butterfly, giving a new skeletal isomer of an MFe4C arrangement.