Thermally driven tetrazine-to-triazole ring contraction mediated by hydroxylammonium cations

Abstract

A nitroimine-functionalized tetrazine exhibits pronounced cation-dependent reactivity with ammonia, hydrazine, and hydroxylamine. While ammonia and hydrazine yield stable salts, hydroxylamine induces a thermally driven tetrazine-to-triazole transformation, revealing that the hydroxylammonium cation governs intermolecular organization and directs divergent reactivity pathways.