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Abstract
The reaction of the hexachlorodiazadiphosphetidine (MeNPCl3)2 with NaOR (R [dbnd] CH2CF3 or C6H5) yields the hexaalkoxy/aryloxy derivatives [MeNP(OR)3]2. On the other hand, the reaction of the N-phenyl derivative with NaOCH2CF3 affords the monophosphazene PhN[dbnd]P(OCH2CF3)3. Spectroscopic data for the new compounds are presented. The structure of the trifluoroethoxy derivative [MeNP(OCH2CF3)3]2 has been confirmed by a single crystal X-ray diffraction study. It crystallizes in the triclinic space group P1 with a = 9.024(2) Å, b = 9.255(2) Å, c = 9.944(2) Å, α = 69.68(2)°, β = 60.16(2)°. γ = 78.88(2)°, and Z = 1. The final conventional unweighted residual is 0.044. The transformation of [MeNP(OCH2CF3)3]2 into its monomer at 110°C and its redistribution reaction with [MeNPF3]2 have been investigated by NMR spectroscopy. The formation of dimeric species appears to be favored by electron withdrawing groups at phosphorus promoting delocalization in the P[sbnd]N[sbnd]P system.