A QUANTITATIVE SCALE FOR THE OXIDIZING STRENGTH OF OXIDATIVE FLUORINATORS

A quantitative scale for the oxidizing strength of oxidative fluorinators has been developed for the first time. This scale is based on relative F+ detachment energies, which were obtained by local density functional calculations, and is anchored to its F+ zero point by an experimental value for KrF+. The oxidizing strength of 36 oxidizers was determined in this manner and shown to be consistent with all of the previously available qualitative experiments. An analysis of the trends in the calculated data reveals some expected but also some highly unexpected features. Thus, the oxidizer strength depends not only on the number of fluorine ligands and the oxidation state and electronegativity of the central atom but also on the presence of free valence electron pairs on the central atom and the geometry of the oxidizer. The heats of formation of these oxidizers were also determined from their F+ detachment energy values.