Metal-free Transformations of Nitrogen-Oxyanions to Ammonia via Oxoammonium Salt

Transformations of nitrogen-oxyanions (NO_x^- ) to ammonia impart pivotal roles in sustainable biogeochemical processes. While metal-mediated reductions of NO_x^- are relatively well known, this report illustrates proton-assisted transformations of NO_x^- anions in the presence of electron-rich aromatics such as 1,3,5-trimethoxybenzene (TMB-H, 1 a) leading to the formation of diaryl oxoammonium salt [(TMB)₂ N⁺ =O][NO₃^- ] (2 a) via the intermediacy of nitrosonium cation (NO⁺ ). Detailed characterizations including UV/Vis, multinuclear NMR, FT-IR, HRMS, X-ray analyses on a set of closely related metastable diaryl oxoammonium [Ar₂ N⁺ =O] species disclose unambiguous structural and spectroscopic signatures. Oxoammonium salt 2 a exhibits 2 e^- oxidative reactivity in the presence of oxidizable substrates such as benzylamine, thiol, and ferrocene. Intriguingly, reaction of 2 a with water affords ammonia. Perhaps of broader significance, this work reveals a new metal-free route germane to the conversion of NO_x  to NH₃ .