A theoretical investigation of the role of the solvent on the structure of the intermediates in solvolytic reactions. Part 4. Methanediazonium ion and methyl fluoride in hydrofluoric acid

Abstract

The effect of a solvent other than water, i.e. hydrofluoric acid, on the dissociation process of CH₃N₂⁺ and CH₃F was investigated by MO theory at the CNDO/2 level of approximation. As in water, CH₃N₂⁺ in HF dissociates without the formation of intermediates, while CH₃F forms stable ion pairs. The structure of dissolved ions and molecules is more affected by water than by HF, and water is more effective in promoting charge transfer and separation, in line with the physical properties of the solvents.