Synthesis and ansa substitution of novel examples of aryl hydrido fluorophosphazenes

The first examples of uncharged aryl substituted fluorinated hydridophosphazenes, N3P3F4(Ar)H [Ar=C6H5 (1), p-ClC6H4 (2)] were obtained in an unprecedented manner upon fluorination of diaryloctachlorobi(cyclophosphazenes) (N6P6Cl8(Ar)2) [Ar=C6H5, p-ClC6H4] using KF in acetonitrile. The compounds (1) and (2) were stable to air and moisture, and were characterized by spectral and analytical methods. Compound (1) on reaction with FcCH2P(S)(CH2OLi)2 (Fc=Ferrocenyl) gave endo (3) and exo (4) isomers of ansa substituted hydridophosphazenes. The crystal structure of (4) was determined and the structure shows the ansa substitution on the phosphazene ring, trans to the phenyl group with the hydridophosphazene ring puckered to a partial chair configuration.