On pyridine chloronium cations

Abstract

We present the first solid-state structural evidence of mono- and bis(pyridine)chloronium cations. The latter was synthesized from a mixture of pyridine, elemental chlorine and sodium tetrafluoroborate in propionitrile at low temperatures. The mono(pyridine) chloronium cation was realized with the less reactive pentafluoropyridine, using ClF, AsF₅, and C₅F₅N in anhydrous HF. During the course of this study, we also investigated pyridine dichlorine adducts and found a surprising disproportionation reaction of chlorine that depended on the substitutional pattern of the pyridine. Electron richer dimethylpyridine (lutidine) derivatives favor full disproportionation into a positively and a negatively charged chlorine atom which forms a trichloride monoanion, while unsubstituted pyridine forms a 1 : 1 py·Cl₂ adduct.