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Aromaticity-promoted oxygen-centered radical stability in α-hydroxy heterocyclics
Jiancang Cao1, Yuanyuan Li2, Wanxi Peng1
1College of Chemistry and Materials, Henan Agricultural University, Zhengzhou, Henan, People's Republic of China. Lu.Lin@henau.edu.cn.
None:
This study investigates the influence of aromaticity on the thermodynamic stability of oxygen-centered radicals. The bond dissociation energy and radical stabilization energy were computed to assess the bond strength and radical stability; the nuclear-independent chemical shift analysis and anisotropy of the induced current density analysis were performed to determine the variations in aromaticity. In this work, the thermodynamic stability of oxygen-centered radicals increases as the aromaticity is enhanced, in sharp contrast to the carbon-centered radicals reported previously. The principal interacting orbital analysis revealed that anti-aromatic radicals exhibit a relatively strong p-π conjugation effect, and spin population analysis suggests that the single-electron distribution in aromatic radicals is more delocalized. However, the strong electron-withdrawing inductive effects of neutral oxygen radicals significantly destabilize the σ-electron skeleton, making the electron-deficient anti-aromatic radicals more reactive.
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