The reactions of lithiated diphosphanes with transition metal chlorides constitute a new general entry to phosphinophosphinidene complexes: the reaction of Cp₂ZrCl₂ (Cp = C₅H₅) with ^tBu₂P–P(SiMe₃)Li (molar ratio ∼1 ∶ 1) yields [μ-(1,2∶2-η-^tBu₂PP){Zr(Cl)Cp₂}₂]; the reaction of Cp₂ZrCl₂ with ^tBu₂P–P(SiMe₃)Li (molar ratio ∼1 ∶ 2) and an excess of PPhMe₂ in DME yields the first terminally bonded phosphinophosphinidene complex, [{Zr(PPhMe₂)Cp₂}(η¹-P–P^tBu₂)].