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

doi:10.1002/cphc.202200867

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 journal › Article › peer-review

4 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 language	English
Journal	ChemPhysChem
DOIs	https://doi.org/10.1002/cphc.202200867
Publication status	Accepted/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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10.1002/cphc.202200867

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

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.",

keywords = "chemical bonding, density functional theory, heterolytic scissions, homolytic scissions, nitrile imine",

author = "Cristian Guerra and Leandro Ayarde-Henr{\'i}quez and Rodr{\'i}guez-N{\'u}{\~n}ez, {Yeray A.} and Adolfo Ensuncho and Eduardo Chamorro",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.",

year = "2023",

doi = "10.1002/cphc.202200867",

language = "English",

journal = "ChemPhysChem",

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T1 - Elucidating the N−N and C−N Bond-breaking Mechanism in the Photoinduced Formation of Nitrile Imine

AU - Guerra, Cristian

AU - Ayarde-Henríquez, Leandro

AU - Rodríguez-Núñez, Yeray A.

AU - Ensuncho, Adolfo

AU - Chamorro, Eduardo

PY - 2023

Y1 - 2023

N2 - 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.

AB - 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.

KW - chemical bonding

KW - density functional theory

KW - heterolytic scissions

KW - homolytic scissions

KW - nitrile imine

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DO - 10.1002/cphc.202200867

M3 - Article

AN - SCOPUS:85150594509

SN - 1439-4235

JO - ChemPhysChem

JF - ChemPhysChem

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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