Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability

MOLINA, FRANCO L.; JARA-TORO, RAFAEL A.; NOBLE, JENNIFER A.; DEDONDER-LARDEUX, CLAUDE; JOUVET, CHRISTOPHE; PINO, GUSTAVO A.

Chemphyschem

WILEY-V C H VERLAG GMBH

Año: 2023 vol. 24

1439-4235

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O−…H+…−OCO) features a single local minima, with the proton localized on the O− group (OH…−OCO). However, the structure with the proton localized on the −OCO group (O−…HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…−OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…−OCO isomer decarboxylate without barrier, while the radicals produced from the O−…HOCO isomer are stable.