Abstract
Topological analysis of the electron localisation function (ELF), natural bond orbital and Wiberg bond index calculations have been applied to study the electronic structure of the oxaziridine molecule with a special focus on the nitrogen-oxygen bond. The calculations have been performed at the DFT(B3LYP, CAM-B3LYP, ωB97XD, M06-L, M06-2X) and post-Hartree-Fock (CCSD(T) and CASSCF) computational levels with applied aug-cc-pVTZ basis set. Nature of N-O bonding has been characterised by two resonance forms, N+O− and N−O+, owing to a very small population (< 0.60e) of the bonding basin V(N,O), localised in the ELF field for the N-O region. The importance of electron correlation effects for the description of the N-O bonding has been observed in the CASSCF calculations. The orbital description (Wiberg, NBO) differs from topological characterisation, indicating a single N-O bond.
Highlights
Oxaziridine, H2CN(H)O, is an unstable molecule with triangular heterocycle, containing carbon, oxygen and nitrogen
The current research increases our knowledge about the nature of the nitrogen-oxygen bonding in molecular systems
The obtained results allow to explain the unstable nature of the oxaziridine through specific nature of the N-O bond
Summary
Oxaziridine, H2CN(H)O, is an unstable molecule with triangular heterocycle, containing carbon, oxygen and nitrogen (see Fig. 1). Due to high electronegativity of oxygen and nitrogen, three-membered ring is relatively weak and can break [1]. In nucleophilic substitution with small steric bulk, a nucleophile tends to attack nitrogen first, leading to ring opening. Most of the research was performed for oxaziridine intermediate or its derivatives due to its unstable nature [3, 4]. First oxaziridine derivatives were reported by Emmons [5]. Weak N-O bond can lead to oxygen and nitrogen substitution in many chemical reactions, such as formation of stereospecific α-hydroxyketones [6,7,8]. Industrial production of hydrazine is performed through imine oxidation with hydrogen peroxide to oxaziridine [9].
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