Fluorinated Hypofluorites and Hypochlorites

J. M. Shreeve, Fluorinated Hypofluorites and Hypochlorites, Advan. Inorg. Chem. Radiochem. 26 [1983] 119/68, 121/3. 

Progress in the preparation and isolation of different hypohaiites [92] results in a substantial number of publications exploring the addition of these materials to fluoroolefins. In contrast to addition of hypofluorites, which at this time is viewed as a radical process, a polar mechanism was proposed for addition of poly-fluorinated hypochlorites and hypobromites to olefins. Reactions of fluoroolefins... 

It has been known that highly fluorinated alkyl-hypochlorites and hypofluorites RFOX (with X=C1 or F) are of synthetic value in the preparation of many fluorine... 

The electrophihc nature of COF2 is beneficial in the reaction of carbonyl difluoride with CsF, which produces trifluoromethyl hypofluorite (CF3OF) with fluorine and triflnoromethyl hypochlorite (CF3OCI) with chlorine monoflnoride. Both reactions imply the presence of the triflnoromethoxide anion as an intermediate. 

The preparation of the first perfluoroalkyl hypochlorites via caesium fluoride or Lewis acid (HF, BF, or AsFj) catalysed addition of chlorine monofluoride across the 0=0 bond of a perfluorocarbonyl compound, first reported in 1968 and a modification of an excellent general route to perfluoroalkyl hypofluorites employing fluorine and carbonyl compounds, has now been described in detail > the addition proceeds smoothly and in almost quantitative yield at low temperatures, e.g. 

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