Chemical Properties of an Aryloxenium Cation with a Triplet Electronic Ground State

Aryloxenium cations contain a formally positively-charged, monovalent oxygen atom with an incomplete electron shell. In spite of this unusual structural element, they are key intermediates in many important processes, such as biological oxidation reactions and the industrial generation of thermoplastics. However, the development of new applications is hindered by the lack of knowledge on their fundamental chemical properties. While most past studies have focused on aryloxenium cations with singlet electronic ground states, minor structural modifications can produce aryloxenium cations that have a triplet ground state. Unfortunately, examination of the reactivity of triplet aryloxenium cations is limited to just two studies that reported the detection of H atom abstraction from solvents. A detailed kinetic reactivity study involving cyclohexane, allyl iodide and dimethyl disulfide reagents is reported here for an aryloxenium cation with a triplet electronic ground state, the 2-amino-4-pyridyloxenium cation.