期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 23, 页码 7519-7525出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b04414
关键词
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资金
- NSF [CHE-1359809]
- ANR [ANR-14-CE06-0013-01]
- Labex Arcane [ANR-11-LABX-0003-01]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1359809] Funding Source: National Science Foundation
A series of monomeric (amino) (carboxy) radicals featuring carbonyl substituents with increasing electron-withdrawing properties (3a, phenyl; 3b, 3,5-bis(trifluoromethyl)phenyl; 3c, perfluorophenyl; 3d, heptafluoropropyl; 3e, 2H-pyrroliumyl) were synthesized in two or three steps from stable cyclic (allcy)(amino)carbenes (CAACs). Although (amino) (carboxy) radicals had been previously considered as highly air-sensitive, some of these compounds feature half-lives of hours (3d), and even days (3c and 3e) in well-aerated solutions. DFT calculations show that (amino)(carboxy) radicals evolve from C-centered radical to ambidentate CO-radicals when increasing the electron-withdrawing properties of the carbonyl substituent. This is paralleled with a destabilization of the peroxide resulting from the addition of dioxygen to the radical. This latter reaction is even predicted to be endothermic for substituents with Hammett constant sigma(p) > 0.2.
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