An X-ray crystallorgraphic study of the reagent Ph3PCl2; not charge-transfer, R3P–Cl–Cl, trigonal bipyramidal or [R3PCl]Cl but an unusual dinuclear ionic species, [Ph3PCl+⋯Cl–⋯+CIPPH3]Cl containing long Cl–Cl contacts

Abstract

An X-ray crystallographic study of the reagent Ph₃PCl₂ reveals it to be [Ph₃PCl⁺⋯Cl^–⋯⁺ClPPh₃]Cl and not trigonal bipyramidal, molecular charge-transfer Ph₃P–Cl–Cl or the simple ionic species [Ph₃PCl]Cl; this contrasts with the conclusions from all previous spectroscopic data recorded on compounds of stoichiometry R₃PCl₂ by earlier workers, and represents the first compound of this formula to be crystallographically characterised.