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The kinetically stable triazatriphosphorinyl and tetraazatetra-phosphorocinyl azides 3 and 4 are prepared from the corresponding chlorides 1, 2 with sodium azide. 3 and 4 react with phosphanes to yield the λ5 -diphosphazenes 5a-d. By the reaction of 1 or 2 with KCN the nitriles 6 and 7 are formed. -The new compounds are characterized on the basis of IR and mass spectra.