The diiminodiphosphine (Lim) and diaminodiphosphines (L-NH and L-NMe) with a bifunctional PNNP ligand framework have been employed to host two [GeCl]+ units leading to the formation of bis(chlorogermyliumylidene) 1–3, respectively. The synthetic route involves a 1 : 2 stoichiometric reaction between the PNNP ligand and GeCl2·dioxane and the subsequent addition of two equivalents of chloride abstracting agent. Compound 1 is unstable towards coordinating solvents and Lewis bases, resulting in the displacement of the GeCl unit and the formation of rearranged products 4 and 5. However, the diaminodiphosphine coordinated Ge(II) bis(monocation)s 2 and 3 proved to be stable and revealed their electrophilic behaviour towards the Lewis bases studied.
