Main-group derivatives of the highly electronegative OIF4O-group

The oxygen-bonded derivatives FXeOIOF4 and Xe(OIOF4)2, including all isomers derived from cis-trans isomerism associated with the OIF4O-group, have been observed as the reaction products in IO2F3/XeF2 solution mixtures by 19F and 129Xe NMR spectroscopy. The 129Xe chemical shifts have been used to establish that the OIF4O-group is the most electronegative group known next to fluorine. In addition, the Xe(IV) derivative F3XeOIOF4, has also been characterized in solution.Generally, the isolation of OIF4O-derivatives may not be accomplished by routes analogous to those used in the syntheses of -OTeF5 derivatives. For example, direct reaction of HOIOF4 and XeF2 may lead to violent detonations which arise from the formation of the shock-sensitive hypofluorite, FOIOF4. The formation of FOIOF4 is circumvented by avoiding the use of fluoride precursors. Thus, it is possible to synthesize and isolate cis,cis- Xe(OIOF4)2 by displacement of volatile HOTeF5 from Xe(OTeF5)2 by reaction with a stoichiometric amount of the strong protonic acid HOIOF4. The solid state low-temperature Raman spectrum as well as the 19F and 129Xe NMR spectra are consistent with the proposed cis,cis-structure.