Cyano derivatives of some organochlorophosphate(V) ions

Abstract

Reaction of excess AgCN with the organochlorophosphate(V) ions [PRCl₅]^–(R = Ph or Me) leads to the formation of [PPhCl₂(CN)₃]^–(all three isomers) and [PMe(CN)₅]^– respectively; salts containing these ions have been isolated, and characterised by elemental analysis and ³¹P n.m.r. spectroscopy. Several intermediate six-co-ordinate phosphorus complexes have been identified spectroscopically, and isomeric configurations have been assigned by the method of pairwise interactions. The agreement between calculated and observed shift values is less good than in six-co-ordinate phosphorus(V) systems with substituents other than cyanide, possibly because of distortions from regular octahedral geometry.