期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 47, 页码 25082-25088出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202110870
关键词
anti-aromaticity; free radicals; stereoelectronic effects; zwitterions
资金
- NSF [NSF CHE 2055335, CHE 1764235]
- NSF under MRI grant [CBS 1229081]
- NSF under CRI grant [1205413]
By conjugating formally antiaromatic substituents to the free radical, a new strategy to stabilize free radicals electronically has been described. This strategy successfully stabilizes radicals by providing antiaromaticity relief to the substituent, but only if the antiaromatic substituent is constrained to be planar by synthetically imposed conformational restraints. This work leads to the counterintuitive finding that increasing the antiaromaticity of the radical substituent leads to greater radical stability, providing proof of concept for a new stereoelectronic approach for stabilizing free radicals.
A new strategy to stabilize free radicals electronically is described by conjugating formally antiaromatic substituents to the free radical. With an antiaromatic substituent, the radical acts as an electron sink to allow configuration mixing of a low-energy zwitterionic state that provides antiaromaticity relief to the substituent. A combination of X-ray crystallography, VT-EPR and VT-UV/Vis spectroscopy, as well as computational analysis, was used to investigate this phenomenon. We find that this strategy of antiaromaticity relief is successful at stabilizing radicals, but only if the antiaromatic substituent is constrained to be planar by synthetically imposed conformational restraints that enable state mixing. This work leads to the counterintuitive finding that increasing the antiaromaticity of the radical substituent leads to greater radical stability, providing proof of concept for a new stereoelectronic approach for stabilizing free radicals.
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