The reaction of intramolecular stannylene phosphorus Lewis pairs with heavier dichlorides of group 14 (GeCl2, SnCl2, PbCl2) is reported. Phosphine base stabilized stannyl germylenes/stannylenes were formed by the oxidative addition of an E–Cl bond to the stannylene tin atom (E = Ge, Sn). In solution, a dynamic equilibrium between two diastereomeric configurations was observed. With PbCl2 a redox reaction towards elemental lead and the dichlorinated tin(IV) compound was found. All compounds were characterized by X-ray diffraction, NMR spectroscopy and elemental analysis.
