A convenient preparative approach to low-valent phosphorus-rich oligomers is presented. Ligand substitution reactions involving anionic diphosphine ligands of the form [(PR2)(2)N](-) and [(PPh2)(2)C5H3](-) and a triphosphenium bromide P(I) precursor result in the formation of phosphorus(I)-containing heterocycles, several of which are of types that have never been prepared before. The methodology described also allows for the preparation of the known heterocycle cyclo-[P(PPh2)N(PPh2)](2) in better yields and purity than the synthetic approach reported previously. Preliminary reactivity studies demonstrate the viability of such zwitterionic oligomers as multidentate ligands for transition metals.