HETEROATOM CHEMISTRY, vol.5, no.4, pp.349-357, 1994 (SCI-Expanded)
The reactions of Cl3P=N-P(O)Cl-2 (1) with primary and secondary amines have been studied. The following monophosphazenes, (RRN)(3)P=N-P(O)(NRR)(2), and bis(phosphinoyl)amines, [(RRN)(2)P(O)]2NH were isolated: NRR = NHCH(2)Ph, NEt(2), NH(CH2)(2)CH3 groups for monophosphazenes, and NEt(2), NH(CH2)(2)CH3 for phosphinoyl amines. The unexpected geminal phosphazene, Cl(RRN)(2)P=N-P(O)Cl-2, {RRN = N[CH(CH3)(2)](2)}, was also obtained in moderate yield. The spectral data (IR, H-1, C-13, and P-31 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.