Metaphosphates with imido and chalcogenido substituents attached to a central phosphorus(V) center form ambidentate dimeric dianions that are potential components of metal-containing coordination polymers. This review summarizes the syntheses and structures of s-, p- and d-block metal complexes of these versatile ligands and their bis(amido)cyclodiphosph(V/V)azane precursors. The synthesis and structures of metal complexes of the corresponding cyclodiphosph(III/V)azane ligands are also discussed.