Synthesis and ansa substitution of novel examples of aryl hydrido fluorophosphazenes

Abstract

The first examples of uncharged aryl substituted fluorinated hydridophosphazenes, N 3P 3F 4(Ar)H [Ar=C 6H 5 ( 1), p-ClC 6H 4 ( 2)] were obtained in an unprecedented manner upon fluorination of diaryloctachlorobi(cyclophosphazenes) (N 6P 6Cl 8(Ar) 2) [Ar=C 6H 5, p-ClC 6H 4] 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 FcCH 2P(S)(CH 2OLi) 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.