Here we report the syntheses of rare examples of five‐coordinated P (V) ‐phosphates. Oxidation of the phosphazenium phosphoranide EtP 4 HP (C 2 F 5) 2 F 2 (EtP 4 H = (Et 2 N) 3 P=N 3 P=N (H) t Bu) with N 2 O or S 8 affords the corresponding oxophosphate EtP 4 HP (C 2 F 5) 2 F 2 O and thiophosphate EtP 4 HP (C 2 F 5) 2 F 2 S. The oxophosphate was also prepared starting from P (C 2 F 5) 3 F 2 as a precursor. Reaction of P (C 2 F 5) 3 F 2 with water presumably yields the oxonium salt of the hydroxophosphate P (C 2 F 5) 3 F 2 (OH) −, which undergoes a cation exchange upon treatment with PPh 4 Cl, furnishing PPh 4 P (C 2 F 5) 3 F 2 (OH). Treatment of the latter with substoichiometric amounts of a strong base initiates HC 2 F 5 elimination yielding PPh 4 P (C 2 F 5) 2 F 2 O. In addition, computational studies were performed to elucidate the description of the oxo‐ and thiophosphate with Lewis structures.
Hartmann et al. (Sun,) studied this question.