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Metal‐free Transformations of Nitrogen‐Oxyanions to Ammonia via Oxoammonium Salt
Author(s) -
Sahana Tuhin,
Mondal Aditesh,
Anju Balakrishnan S.,
Kundu Subrata
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105723
Subject(s) - chemistry , salt (chemistry) , metal , ammonia , inorganic chemistry , reactivity (psychology) , nitrogen , nucleophile , medicinal chemistry , polymer chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
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][NO 3 − ] ( 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 [Ar 2 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 NH 3 .