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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université Paris Diderot - 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
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Université Paris Diderot
Université de Paris CNRS, Centre National de la Recherche Scientifique
 
 


Le LEM - Publications: Abstracts

Publication 752

Annu. Rev. Anal. Chem., 7, 537-560, 2014
DOI:10.1146/annurev-anchem-071213-020315
   

 

doi


Concerted proton-electron transfers: fundamentals and recent developments.

Jean-Michel Savéant

Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche, Université Paris Diderot, Sorbonne Paris Cité, CNRS 7591, 75205 Paris Cedex 13, France

Proton-coupled electron transfers (PCET) are ubiquitous in natural and synthetic processes. This review focuses on reactions where the two events are concerted. Semiclassical models of such reactions allow their kinetic characterization through activation versus driving force relationships, estimates of reorganization energies, effects of the nature of the proton acceptor, and H/D kinetic isotope effect as well as their discrimination from stepwise pathways. Several homogeneous reactions (through stopped-flow and laser flash-quench techniques) and electrochemical processes are discussed in this framework. Once the way has been rid of the improper notion of pH-dependent driving force, water appears as a remarkable proton acceptor in terms of reorganization energy and pre-exponential factor, thanks to its H-bonded and H-bonding properties, similarly to purposely synthesized “H-bond train” molecules. The most recent developments are in modeling and description of emblematic concerted proton-electron transfer (CPET) reactions associated with the breaking of a heavy-atom bond in an all-concerted process.

 
   
 
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