Elucidating the N−N and C−N Bond-breaking Mechanism in the Photoinduced Formation of Nitrile Imine

Cristian Guerra, Leandro Ayarde-Henríquez, Yeray A. Rodríguez-Núñez, Adolfo Ensuncho, Eduardo Chamorro

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

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.

Original languageEnglish
JournalChemPhysChem
DOIs
Publication statusAccepted/In press - 2023

Keywords

  • chemical bonding
  • density functional theory
  • heterolytic scissions
  • homolytic scissions
  • nitrile imine

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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