Aminolysis of P‐trichloro‐N‐dichlorophosphorylmonophosphazene and the crystal structure of 1‐(dichlorophosphinyl)‐2‐chloro‐2,2‐bis(diisopropylamino)phosphazene

Abstract

The reactions of Cl3PNP(O)Cl2 (1) with primary and secondary amines have been studied. The following monophosphazenes, (RRN)3PNP(O)(NRR)2, and bis(phosphinoyl)amines, [(RRN)2P(O)]2NH were isolated: NRR = NHCH2Ph, Net2, NH(CH2)2CH3 groups for monophosphazenes, and Net2, NH(CH2)2CH3 for phosphinoyl amines. The unexpected geminal phosphazene, Cl(RRN)2PNP(O)Cl2, {RRN = N[CH(CH3)2]2}, was also obtained in moderate yield. The spectral data (IR, 1H, 13C, and 31P NMR, and MS) are presented. The structure of 1‐(dichlorophosphinyl)‐2‐chloro‐2,2‐bis(diisopropylamino)phosphazene ( 5) was determined by X‐ray crystallography. The basicities of these and related compounds in nonaqueous nitrobenzene solution were obtained by potentiometric titration. Copyright © 1994 VCH Publishers, Inc.