Two fluorine-substituted phosphoryl pseudohalides including the highly explosive diazide FP(O)(N3)2 and dii-socyanate FP(O)(NCO)2 have been synthesized and fully characterized with IR (gas-phase and noble-gas matrices), Raman (liquid), and NMR (19F and 31P) spectroscopy. The vibrational spectra of FP(O)(N3)2 and FP (O)(NCO)2 were analyzed with the aid of the B3LYP/6