Abstract

In 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.