Measuring Kinetics under Vibrational Strong Coupling: Testing for a Change in the Nucleophilicity of Water and Alcohols.

Autor: Muller C; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France., Mayer RJ; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France.; School of Natural Sciences, Department Chemie, Technical University Munich (TUM), 85748, Garching, Germany., Piejko M; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France., Patrahau B; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France., Bauer V; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France., Moran J; University of Strasbourg, CNRS, ISIS UMR 7006, 67000, Strasbourg, France.; Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 02; Vol. 63 (49), pp. e202410770. Date of Electronic Publication: 2024 Oct 24.
DOI: 10.1002/anie.202410770
Abstrakt: Vibrational Strong Coupling (VSC) has been reported to change the rate of organic reactions. However, a lack of convenient and reliable methods to measure reaction kinetics under VSC makes it challenging to obtain mechanistic insight into its influence, hindering progress in the field. Here, we use recently developed fixed-width optical cavities to obtain large kinetic datasets under VSC with small errors (±1-5 %) in an operationally simple manner using UV/Vis spectroscopy. The setup is used to test whether VSC changes a fundamental kinetic property of polar reactions, nucleophilicity, for water and alcohols, species commonly used in VSC-modified chemistry. We determined the rate constants for nucleophilic capture with a library of benzhydrilium ions as reference electrophiles with and without strong coupling of the nucleophile's key vibrations. For all investigated combinations of electrophiles and nucleophiles, only minor changes in the observed rate constants of the reactions were observed independently of the coupled bands. These results indicate that VSC does not substantially alter the nucleophilicity of water and alcohols, suggesting that polar reactions are modified through other, presently unknown mechanisms. Fixed-width cavities allow for convenient and reproducible UV/Vis kinetics, facilitating mechanistic studies of VSC-modified chemistry.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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