Evidence for Oxonium Ions in Ethereal "Hydrogen Chloride"

Although solutions of hydrogen chloride in ethereal solvents like diethyl ether or dioxane are commonly employed in the laboratory, the solution structure of these reagents has yet to be firmly established. Here, we analyze solutions of ethereal hydrogen chloride or deuterium chloride in toluene, dichloromethane, or in the absence of cosolvent by in situ IR spectroscopy. The resulting spectra are inconsistent with free HCl or often-proposed 1:1 HCl:ether complexes, but closely match the predicted spectra of oxonium ions generated via protonation of diethyl ether. Molecular dynamics simulation of the oxonium chloride complexes provides evidence for an outer-sphere contact ion pair. These results suggest new approaches for tuning the acidity of strong Brønsted acids in organic solvents and demonstrate the importance of conducting spectroscopic measurements under reaction-relevant conditions.