Isolation and characterization of a triplet nitrene DOI Creative Commons
Gengwen Tan, Dongmin Wang, Wang Chen

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 14, 2024

Abstract Free nitrenes of R–N are short-lived intermediates in a variety nitrogen-involved transformations. They feature either singlet ground state or triplet state, depending on the electronic properties substituents R. Triplet arylnitrenes typically undergo facile ring expansion to azacycloheptatetraenes, making their isolation condensed phase highly challenging. Herein, we present synthesis, and characterization an isolable arylnitrene supported by bulky hydrindacene ligand. The high stability is largely attributed sufficient steric hindrance effective electron delocalization imparted supporting Electron paramagnetic resonance spectroscopy conjunction with correlated wavefunction based ab initio calculations unambiguously demonstrated its axial zero-field splitting D = 0.92 cm–1 vanishing rhombicity E/D 0.002. This work not only presents long-sought reaction intermediate, but also provides in-depth insights into mechanisms involving nitrenes.

Language: Английский

Isolation and characterization of a triplet nitrene DOI Creative Commons
Gengwen Tan, Dongmin Wang, Wang Chen

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 14, 2024

Abstract Free nitrenes of R–N are short-lived intermediates in a variety nitrogen-involved transformations. They feature either singlet ground state or triplet state, depending on the electronic properties substituents R. Triplet arylnitrenes typically undergo facile ring expansion to azacycloheptatetraenes, making their isolation condensed phase highly challenging. Herein, we present synthesis, and characterization an isolable arylnitrene supported by bulky hydrindacene ligand. The high stability is largely attributed sufficient steric hindrance effective electron delocalization imparted supporting Electron paramagnetic resonance spectroscopy conjunction with correlated wavefunction based ab initio calculations unambiguously demonstrated its axial zero-field splitting D = 0.92 cm–1 vanishing rhombicity E/D 0.002. This work not only presents long-sought reaction intermediate, but also provides in-depth insights into mechanisms involving nitrenes.

Language: Английский

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