An X-ray crystallographic study of the reagent Ph(3)PCl(2); Not charge-transfer, R(3)P-Cl-Cl, trigonal bipyramidal or [R(3)PCl]Cl but an unusual dinuclear ionic species, [Ph(3)PCl+center dot center dot center dot Cl-center dot center dot center dot(+)ClPPh(3)]Cl containing long Cl-Cl contacts

An X-ray crystallographic study of the reagent Ph(3)PCl(2) reveals it to be [Ph(3)PCl(+)... Cl-...(+)ClPPh(3)]Cl and not trigonal bipyramidal, molecular charge-transfer Ph(3)P-Cl-Cl or the simple ionic species [Ph(3)PCl]Cl; this contrasts with the conclusions from all previous spectroscopic data recorded on compounds of stoichiometry R(3)PCl(2) by earlier workers, and represents the first compound of this formula to be crystallographically characterised.