Hypofluorous acid and acetonitrile: the taming of a reagent

Abstract

The strong oxidant produced by the reaction of elemental fluorine with acetonitrile containing ca. 10% water has been shown to be hypofluorous acid, HOF, which is stabilized by complexing to the solvent. The reaction represents a new and convenient method of preparing and handling HOF, a unique oxygenating reagent. The presence of acetonitrile results in subtle but significant changes in the chemical behavior of the HOF. Vibrational and NMR spectroscopic studies of the solutions resulting from this reaction, as well as of solutions prepared by dissolving neat HOF in dry acetonitrile, have shown that the complex is a 1:1 hydrogen-bridged entity, in which the HOF proton is most likely bonded to the nitrogen atom of the nitrile. The 19F NMR data indicate that the complexation reaction has an equilibrium constant of ca. 3 at room temperature, and that the enthalpy of formation of the complex is −14.3 ± 0.5 kJ mol −1. The success of this method of synthesizing hypofluorous acid is a consequence of the very slow reaction between HOF and low concentrations of water in acetonitrile. This reaction accelerates drastically as the water content increases. As the solution composition approaches 100% water, the rate constant appears to approach a limit of about 0.7 s −1 at 25 °C, which may be the actual rate of reaction of HOF with the water.