Elucidating the N−N and C−N Bond-breaking Mechanism in the Photoinduced Formation of Nitrile Imine
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Fecha
2023-06
Profesor/a Guía
Facultad/escuela
Idioma
en
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Título del volumen
Editor
John Wiley and Sons Inc
Nombre de Curso
Licencia CC
CC BY-NC-ND 4.0 Attribution-NonCommercial-NoDerivatives 4.0 International Deed
Licencia CC
https://creativecommons.org/licenses/by-nc-nd/4.0/
Resumen
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.
Notas
Indexación: Scopus
Palabras clave
Chemical Bonding, Density Functional Theory, Heterolytic Scissions, Homolytic Scissions, Nitrile Imine
Citación
ChemPhysChem. Volume 24, Issue 11. 1 June 2023. Article number e202200867
DOI
10.1002/cphc.202200867