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Exploitation of an old and frequently studied reaction (to obtain new compounds) has proven successful with the system PCl3/P(NMe2)3/AlCl3. Depending on the sequence in which the reaction partners are allowed to react with each other, different products are formed. The most interesting new products are the diphosphoniodiphosphirane ion 1 (the CH2 group comes from the solvent CH2Cl2) and the cyclotetraphosphane ion 2.