TRIFLUOROMETHANESULFONYL HYPOFLUORITE, A HITHERTO UNKNOWN FLUOROXY COMPOUND

Trifluoromethanesulfonyl hypofluorite (CF3SO2OF) has been synthesized by the reaction of fluorosulfuryl hypofluorite (FSO2OF) with cesium trifluoromethanesulfonate. It is the first compound in which a sulfur atom is bonded both to carbon and to an O-F moiety. The compound has a melting point of -87 +/- 2-degrees-C and an extrapolated boiling point of 0 +/- 1-degrees-C. The F-19 NMR spectrum of the compound in CFCl3 at -80-degrees-C shows a CF3 doublet at -71 ppm and a broad OF singlet at +238 ppm. From the latter can be deduced an O-F bond energy of about 145 kJ/mol, comparable to that of FSO2OF. The compound hydrolyses in base to give a mixture of O2 and CF4, along with (presumably) sulfate and trifluoromethanesulfonate. It decomposes thermally in the presence of CsF to yield principally CF3SO2F and OF2 along with (presumably) cesium trifluoromethanesulfonate.