New examples of chlorophosphinochlorophosphonium (4) and chlorophosphinodichlorophosphonium (5) cations have been prepared and spectroscopically characterized. These bifunctional phosphinophosphonium cations offer a new approach to the development of phosphinophosphonium frameworks using reductive coupling reactions and have been exploited as synthons to assemble larger catena-phosphorus cations. The reactions of 4 and 5 with stibine reducing agents have been studied using (31)P NMR spectroscopy and have been shown to produce a variety of new and known frameworks in a facile manner, depending on the reducing agent selection and the stoichiometry of the reaction. New derivatives of frameworks containing three, four, and five phosphorus atoms have been identified by (31)P NMR spectroscopy. Crystals of the [GaCl(4)](-) salt of the five-membered dication 11((i)Pr) have been isolated from the reaction of [4((i)Pr)][GaCl(4)] with SbBu(3), and the solid state structural features and solution state dynamics are comprehensively described in the context of (31)P{(1)H} NMR spectroscopic observations.