Guerra, CristianAyarde-Henríquez, LeandroRodríguez-Núñez, Yeray A.Ensuncho, AdolfoChamorro, Eduardo2024-10-292024-10-292023-06ChemPhysChem. Volume 24, Issue 11. 1 June 2023. Article number e2022008671439-4235https://repositorio.unab.cl/handle/ria/61610Indexación: ScopusIn this study, we revealed the significance of chemical bonding for the photochemically induced mechanism of 2-phenyl tetrazole derivatives generating nitrile imines. The correlated electron localization function shows that the formation of imine nitrile involves two key bond events: (i) the heterolytic C−N breakage taking place in the T1 state and (ii) the homolytic N−N rupture occurring in the T2 excited state. In particular, a cation-radical specie results from the C−N cleavage, whereas the N−N rupture creates a biradical resonant form of imine nitrile. Additionally, we noticed that the substantial pair delocalization of the C−C-N bonded structure could play a significant role in the conversion of the biradical imine nitrile into both the propargylic and allenic forms via the T1→S0 deactivation. © 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.enChemical BondingDensity Functional TheoryHeterolytic ScissionsHomolytic ScissionsNitrile ImineArtículoCC BY-NC-ND 4.0 Attribution-NonCommercial-NoDerivatives 4.0 International Deed10.1002/cphc.202200867