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Published on: April 19, 2019
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.
Aromaticity enhances the thermodynamic stability of oxygen-centered radicals, unlike carbon-centered ones. This finding contrasts previous research and highlights the impact of aromaticity on radical stability.
Area of Science:
- Computational Chemistry
- Organic Chemistry
- Quantum Chemistry
Background:
- Aromaticity significantly influences molecular properties.
- Understanding radical stability is crucial in chemical reactions.
- Previous studies focused on carbon-centered radicals.
Purpose of the Study:
- To investigate the effect of aromaticity on oxygen-centered radical thermodynamic stability.
- To compare the stability trends with previously studied carbon-centered radicals.
- To elucidate the electronic factors governing this stability.
Main Methods:
- Calculation of bond dissociation energy and radical stabilization energy.
- Nuclear-independent chemical shift (NICS) analysis for aromaticity.
- Anisotropy of the induced current density (AICD) analysis.
- Principal interacting orbital (PIO) and spin population analyses.
Main Results:
- Thermodynamic stability of oxygen-centered radicals increases with enhanced aromaticity.
- Anti-aromatic radicals show strong p-π conjugation.
- Spin population analysis indicates greater delocalization in aromatic radicals.
- Electron-withdrawing inductive effects destabilize the σ-electron skeleton.
Conclusions:
- Aromaticity is a key factor in stabilizing oxygen-centered radicals.
- The observed trend contrasts with carbon-centered radicals.
- Electronic effects, including p-π conjugation and inductive effects, dictate radical reactivity.
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