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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université de Paris - Paris France

   
 
Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie
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Le LEM - Publications: Abstracts

Publication 902

Chem. Sci., 142 (4), 1006-1010, 2019
DOI:10.1039/C9SC05147C
   
doi

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

Cyrille Costentin, and Jean-Michel Savéant

Département de Chimie Moléculaire, Université Grenoble-Alpes, CNRS, UMR 5250, 38000 Grenoble, France
Laboratoire d’Electrochimie Moléculaire, Université de Paris, CNRS, UMR 7591, 15 Rue Jean-Antoine de Baïf, F-75013 Paris, France

A recent remarkable study of the CH 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.

 
   
 
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