Excited-state antiaromaticity relief drives facile photoprotonation of carbons in aminobiphenyls.
Chem Sci
; 15(14): 5225-5237, 2024 Apr 03.
Article
em En
| MEDLINE
| ID: mdl-38577382
ABSTRACT
A combined computational and experimental study reveals that ortho-, meta- and para-aminobiphenyl isomers undergo distinctly different photochemical reactions involving proton transfer. Deuterium exchange experiments show that the ortho-isomer undergoes a facile photoprotonation at a carbon atom via excited-state intramolecular proton transfer (ESIPT). The meta-isomer undergoes water-assisted excited-state proton transfer (ESPT) and a photoredox reaction via proton-coupled electron transfer (PCET). The para-isomer undergoes a water-assisted ESPT reaction. All three reactions take place in the singlet excited-state, except for the photoredox process of the meta-isomer, which involves a triplet excited-state. Computations illustrate the important role of excited-state antiaromaticity relief in these photoreactions.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Chem Sci
Ano de publicação:
2024
Tipo de documento:
Article