Difluoramino radical

Jhe remarkable stability of the difluoramino radical which has recently been established quantitatively (8,14) was presaged by its early chemistry. In retrospect it is apparent that the formation of tetrafluorohydrazine from nitrogen trifluoride under hot tube conditions (4) involved the formation of the difluoramino radical, from which it is more diflScult to remove another fluorine than from nitrogen trifluoride. At the time of the original synthesis, however, it could only be marveled at that N2F4, a compound much closer to nitrogen than NF3, would survive conditions that decomposed the latter. 

It was also observed that N2F4 decomposed in moist air to produce various nitrogen oxides. The origin of this reaction is undoubtedly the coupling of difluoramino radicals with oxygen, since imdissociated N2F4 should be unaffected by air. 

Difluoramino radicals also abstract hydrogen from aliphatic aldehydes to produce difluoramine. In addition, the acyl radical thus generated couples with an NF2 radical to produce a new class of organic compounds, the N,N-difluoramides... 

Difluoramino radicals combine with a variety of other radicals, with the product stability apparently directly related to the stability of the substrate radical. For instance, nitric oxide and NF2 form a compound, difluoronitrosamine, only at low temperatures (3) at room temperature and atmospheric pressure the two radicals do not interact. Chlorine and N2F4 react under the influence of ultraviolet light to produce chlorodifluoramine, CINF2 (13). The equilibrium reaction is favored by high concentrations of chlorine and by high temperature (80° C). Because of this unfavorable equilibrium, the reaction of difluoramine and boron trichloride provides a more satisfactory route to chlorodifluoramine (11). 

The discovery of tetrafluorohydrazine and of its dissociation into difluoramino free radicals has opened a new area of both organic and inorganic chemistry. On the basis of the chemistry so far reported it may be assumed that a wide variety of fluoronitrogen compounds will soon be available for chemical investigation. 

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