Speaker
Description
Vibrational Strong Coupling (VSC) has recently been shown to alter the rates and selectivity of polar chemical reactions –reactions in which electrophiles and nucleophiles combine. However, measuring reliable reaction kinetics under VSC remains an important challenge which hinders our ability to know which specific elementary properties of polar reactions are affected by VSC. We herein set out to test whether VSC influences the nucleophilicity of alcohols and water, which are commonly involved species in previous studies on VSC. We determined the rate constants for the nucleophilic capture of the nucleophiles with a library of benzhydrylium ions as reference electrophiles with and without strong coupling of the nucleophile’s key vibrations. Using recently developed fixed-width cavities enabled the obtention a large kinetic dataset with remarkably small errors. For all investigated combinations of electrophiles and nucleophiles, only small changes in the rate constants of the reactions were observed independently of the coupled bands. These results suggest that VSC does not substantially alter the nucleophilicity of water and alcohols, suggesting that polar reactions are modified through other, presently unknown, mechanisms.
