Chlorine fluoride oxide

The structures of the chlorine oxide fluorides are summarized in Fig. 17.26, together with those of related cationic and anionic species formed from the neutral molecules by gain or loss or F . The first conclusive evidence for free FCIO in the gas phase came in 1972 during a study of the hydrolysis of CIF3 with substoichiometric amounts of H2O in a flow reactor ... 

Figure 17.26 Structures of chlorine oxide fluorides and related cations and anions.

Despite several attempts at synthesis, there is little or no evidence for the existence of FBrO, p3Br02 or FsBrO. The bromine oxide fluorides are somewhat less thermally stable than their chlorine analogues and somewhat more reactive chemically. The structures are as already described for the chlorine oxide fluorides (Fig. 17.26). 

Chlorine Oxide Fluoride. The only member of the halogen oxide fluoride class is chlorine oxide fluoride (6). It forms a solid that melts to a red liquid at —70 °C. In the gaseous state, it is thermally unstable and decomposes to give FCIO2 and CIF. It can be made by the hydrolysis of CIF3 with substoichiometric amounts of H2O in a flow reactor. It is also produced by photolysis of a mixture of CIF and O3 in Ar at 4 15K. 

The electronic absorption spectra of molecular O2F2 and of the radical O2F have been measured in liquid Ar and in other solvents in the region 190—600 nm/° An analysis of the data concerning the nature of the unstable violet and blue compounds that were first reported in 1962 by Streng and Grosse suggests that the colours are due to oxygen fluoride radicals, such as O2F, and not to chlorine oxide fluorides. Thus, it has now been shown that intensely coloured species are formed by O2 salts in liquid HF these species show the same characteristics as the violet and blue compounds . 

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