title: A Serendipitous Rendezvous with a Four-Center Two-Electron Bonded Intermediate in the Aerial Oxidation of Hydrazine.
abstract: 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.
authors.affiliation: Raman Centre for Atomic Molecular and Optical Sciences, Indian Association for the Cultivation of Science, 2A & 2B, Raja S.C. Mullick Road, Kolkata, 700032, India.
authors.forename: Ambar
authors.initials: A
authors.lastname: Banerjee
authors.affiliation: Raman Centre for Atomic Molecular and Optical Sciences, Indian Association for the Cultivation of Science, 2A & 2B, Raja S.C. Mullick Road, Kolkata, 700032, India.
authors.forename: Gaurab
authors.initials: G
authors.lastname: Ganguly
authors.affiliation: Raman Centre for Atomic Molecular and Optical Sciences, Indian Association for the Cultivation of Science, 2A & 2B, Raja S.C. Mullick Road, Kolkata, 700032, India.
authors.forename: Lisa
authors.initials: L
authors.lastname: Roy
authors.affiliation: Department of Molecular Theory and Spectroscopy, Max-Planck Institute for Chemical Energy Conversion, Room: 503, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
authors.forename: Shubhrodeep
authors.initials: S
authors.lastname: Pathak
authors.affiliation: Raman Centre for Atomic Molecular and Optical Sciences, Indian Association for the Cultivation of Science, 2A & 2B, Raja S.C. Mullick Road, Kolkata, 700032, India. rcap@iacs.res.in.
authors.forename: Ankan
authors.initials: A
authors.lastname: Paul
keywords: aromaticity; dioxygen activation; molecular dynamics; multicenter bonding; spin-orbit coupling