Reaction of Xenon Difluoride. Part II. Oxidative-fluorination of Phosphorus and Iodine Compounds and Cleavage of Silicon–Sulfur and Silicon–Nitrogen Bonds

Abstract

Reaction of alkyl(aryl)phosphines with xenon difluoride gives alkyl(aryl)hydridofluorophosphoranes which were characterized by proton and fluorine n.m.r. spectroscopy. With phenylchlorophosphines, substitution of chlorine by fluorine accompanied oxidative-fluorination to give phenylfluorophosphoranes, (C 6 H 5 ) n PF 5−n . With tert-butylchlorophosphines, chlorination of the tert-butyl group accompanied oxidative-fluorination, and a mixture of products was obtained. Reaction of xenon difluoride with methyl iodide gives methyliodine(III) difluoride, characterized by proton and fluorine n.m.r. spectroscopy.Silicon–sulfur and silicon-nitrogen bonds are cleaved by xenon difluoride and an intermediate containing a xenon–nitrogen bond is postulated.Reaction of xenon difluoride with hexafluoroacetone, perfluoropinacol, or disodium perfluoropinacolate failed to give stable xenon esters.