Hydrogen and proton exchange at carbon. Imbalanced transition state and mechanism crossover - Archive ouverte HAL
Article Dans Une Revue Chemical Science Année : 2019

Hydrogen and proton exchange at carbon. Imbalanced transition state and mechanism crossover

Résumé

A recent remarkable study of the C-H oxidation of substituted fluorenyl-benzoates together with the transfer of a proton to an internal receiving group by means of electron transfer outer-sphere oxidants, in the noteworthy absence of hydrogen-bonding interactions, is taken as an example to uncover the existence of a mechanism crossover, making the reaction pass from a CPET pathway to a PTET pathway as the driving force of the global reaction decreases. This was also the occasion to stress that considerations based on "imbalanced" or "asynchronous" transition states cannot replace activation/ driving force models based on the quantum mechanical treatment of both electrons and transferring protons.

Domaines

Chimie
Fichier principal
Vignette du fichier
c9sc05147c.pdf (849.56 Ko) Télécharger le fichier
Origine Fichiers éditeurs autorisés sur une archive ouverte
Licence

Dates et versions

hal-04690041 , version 1 (06-09-2024)

Licence

Identifiants

Citer

Cyrille Costentin, Jean-Michel Savéant. Hydrogen and proton exchange at carbon. Imbalanced transition state and mechanism crossover. Chemical Science, 2019, 11 (4), pp.1006 - 1010. ⟨10.1039/c9sc05147c⟩. ⟨hal-04690041⟩
18 Consultations
6 Téléchargements

Altmetric

Partager

More