The preparation of bromyl fluoride BrO2F by several methods is described as well as its reaction with KF to give K[BrF2O2]. The Raman spectrum of BrO2F has been interpreted in terms of a pyramidal structure. The preparation of bromosyl trifluoride BrOF3 by the reaction of K[BrF4O] with HF is described together with some of its properties. The 19F n.m.r. spectrum of molten BrOF3 and its solutions in SO2ClF and SO2F2 have been recorded and interpreted in terms of fluorine exchange. The Raman spectrum is interpreted on the basis of association in the liquid, solid, and in HF solution. The hydrolysis of BrF5 and the reactions of BrF5 with IO2F, IOF3, and I2O5 produce BrO2F but not BrOF3, whereas the reaction of BrF5 with IO2F3 produces a mixture of BrO2F and BrOF3. The compound BrO2F is fluorinated to BrOF3 and then to BrF5 by KrF2, but no bromine(VII) species are formed.
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