Novel hexacoordinated phosphate anions consisting of a central phosphorus(v) atom and at least one tetrachloropyrocatechol ligand can be simply prepared in modest to decent yields (37-71%) as their dimethylammonium salts following a one-pot process and with simple, usually commercially available, starting materials. A variety of symmetrical diones (α-diketones or ortho-quinones) can be used in this protocol and the structurally-diverse products are chemically stable when two tetrachloropyrocatechol ligands surround the P atom.