Hydration of Phenylium: Oxonium or Carbenium Ion Formation?
The hydration of the phenylium ion (C 6 H 5 + ) is investigated to determine whether the most abundant product structure is best described as an oxonium (O‐protonated phenol) or carbenium (ring‐protonated phenol) ion. Using a combination of infrared multiple‐photon dissociation spectroscopy at the FELIX facility, collision‐induced dissociation experiments, and quantum chemical calculations, we have characterized the reaction products formed upon the addition of water to phenylium. The IR fingerprint of the hydrated ion reveals dominant spectral features consistent with carbenium isomers, particularly the ortho and par a forms, rather than the oxonium isomer. Reactivity measurements and branching ratios of the reaction between water and C 6 H 5 + produced by vacuum ultraviolet (VUV) dissociative photoionization of nitrobenzene at the SOLEIL synchrotron facility, as a function of internal energy show that protonated phenol forms efficiently in the gas phase. Computational modeling of the potential energy surface supports the preferential formation of carbenium structures and maps the key isomerization and dissociation pathways.
Authors
- Bérenger Gans (ORCID: https://orcid.org/0000-0001-9658-2436)
- Jean‐Christophe Loison (ORCID: https://orcid.org/0000-0001-8063-8685)
- Giel Berden (ORCID: https://orcid.org/0000-0003-1500-922X)
- Laura Finazzi (ORCID: https://orcid.org/0009-0009-5675-7890)
- Anne P. Rasmussen (ORCID: https://orcid.org/0000-0003-1093-6163)
- Ugo Jacovella (ORCID: https://orcid.org/0000-0003-2152-261X)
- Corentin Rossi (ORCID: https://orcid.org/0000-0002-5903-9933)
- Nandana Pattathadathil
- Roland Thissen
- Jos Oomens
- Christian Alcaraz
Institutions
- Centre National de la Recherche Scientifique (FR)
- Radboud University Nijmegen (NL)
- Université de Bordeaux (FR)
- University of Trento (IT)
- Aarhus University (DK)
- Synchrotron soleil (FR)
- Radboud University Medical Center (NL)
- Institut des Sciences Moléculaires (FR)
- Radboud Institute for Molecular Life Sciences (NL)
- Laboratoire de Chimie Physique (FR)
- Institut des Sciences Moléculaires d'Orsay (FR)
- Institut de Chimie Moléculaire et des Matériaux d'Orsay (FR)
- Institut Polytechnique de Bordeaux (FR)
Publication Details
- Journal
- ChemistryEurope
- Published
- 2026-04-01
- DOI
- https://doi.org/10.1002/ceur.70232
- Primary Topic
- Chemical Reactions and Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Villum Fonden
- Agence Nationale de la Recherche
- Nederlandse Organisatie voor Wetenschappelijk Onderzoek