A Serendipitous Rendezvous with a Four‐Center Two‐Electron Bonded Intermediate in the Aerial Oxidation of Hydrazine

Oxidation by dioxygen has a rich repertoire of mechanistic intricacies. Herein, we report a hitherto unknown paradigm of dioxygen activation reaction which propagates through a four center two electron (4c–2e) bound species. Using static DFT and ab initio quantum chemical techniques we have unraveled the oxidation pathway for hydrazine and its methylated analogues by dioxygen which involves formation of this unconventional 4c–2e bonded species en route to the oxidation products. Inconvertible evidence in favor of such an unprecedented dioxygen activation route is provided by capturing the events of formation of the 4c–2e species in aqueous phase for hydrazine and its congeners and the experimentally observed products from the respective 4c–2e species, like H₂O₂ and N₂H₂, diazene in the case of hydrazine using Car–Parrinello molecular dynamics simulations.