Investigation of Dissociative Electron Transfer Mechanisms and Reactivity Patterns through Kinetic Amplification by a Chain Process

2000 ◽  
Vol 122 (23) ◽  
pp. 5623-5635 ◽  
Author(s):  
Cyrille Costentin ◽  
Philippe Hapiot ◽  
Maurice Médebielle ◽  
Jean-Michel Savéant
Keyword(s):  
Electron Transfer ◽  
Chain Process ◽  
Dissociative Electron Transfer ◽  
A Chain ◽  
Transfer Mechanisms

Hydrogen vs. electron transfer mechanisms in the chain decomposition of phenacyl bromides. Use of isotopic labeling as a mechanistic probe

1996 ◽  
Vol 74 (9) ◽  
pp. 1724-1730 ◽  
Author(s):  
Jocelyn Renaud ◽  
J. C. Scaiano
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Key Words ◽  
Hydrogen Transfer ◽  
Isotopic Labeling ◽  
Chain Reaction ◽  
Phenacyl Bromides ◽  
Mechanistic Probe ◽  
A Chain ◽  
Transfer Mechanisms

Ring-substituted α-bromoacetophenones react with alcohols in a chain reaction leading to the corresponding acetophenone, HBr, and the carbonyl compound from oxidation of the alcohol. Two different mechanisms, involving hydrogen or electron transfer by ketyl radicals, have been proposed in order to accommodate the unusual selectivities of these reactions. By studying the efficiency of isotope incorporation from deuterated alcohols, it has been possible to determine the relative contributions from both mechanisms. For example, electron transfer dominates in the case of 2-propanol, while hydrogen transfer is more important for methanol. The results demonstrate that ring substitution in the starting ketone is not a main contributing factor in the discrimination between the two mechanisms. The only parameter that seems to be playing a major role is the nature (reducing strength) of the ketyl radicals. Key words: dehydrobromination, charge transfer, isotope effect, ketyl radicals.

scholarly journals Modeling biofilms with dual extracellular electron transfer mechanisms

2013 ◽  
Vol 15 (44) ◽  
pp. 19262 ◽  
Author(s):  
Ryan Renslow ◽  
Jerome Babauta ◽  
Andrew Kuprat ◽  
Jim Schenk ◽  
Cornelius Ivory ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Extracellular Electron Transfer ◽  
Transfer Mechanisms

THEORETICAL STUDIES ON THE COUPLING INTERACTIONS AND SELF-EXCHANGE REACTION MECHANISMS IN THE COMPLEXES OF NO WITH ONH AND NOH

2008 ◽  
Vol 07 (03) ◽  
pp. 435-446 ◽  
Author(s):  
PING LI ◽  
XIAOYAN XIE ◽  
YUXIANG BU ◽  
WEIHUA WANG ◽  
NANA WANG ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Exchange Reaction ◽  
Reaction Mechanisms ◽  
Natural Bond Orbital ◽  
Theoretical Studies ◽  
Exchange Reactions ◽  
Electron Transfer Mechanism ◽  
Proton Coupled Electron Transfer ◽  
Planar Geometries ◽  
Transfer Mechanisms

The coupling interactions and self-exchange reaction mechanisms between NO and ONH (NOH) have been systematically investigated at the B3LYP/6-311++G** level of theory. All the equilibrium complexes are characterized by the intermolecular H-bonds and co-planar geometries. The cisoid NOH/ON species is the most stable one among all the complexes considered due to the formation of an N – N bond. Moreover, all the cisoid complexes are found to be more stable than the corresponding transoid ones. The origin of the blueshifts occurring in the selected complexes has been explored, employing the natural bond orbital (NBO) calculations. Additionally, the proton transfer mechanisms for the self-exchange reactions have been proposed, i.e. they can proceed via the three-center proton-coupled electron transfer or five-center cyclic proton-coupled electron transfer mechanism.

Electron transfer mechanisms

1998 ◽  
Vol 2 (2) ◽  
pp. 235-243 ◽  
Author(s):  
DN Beratan ◽  
SS Skourtis
Keyword(s):  
Electron Transfer ◽  
Transfer Mechanisms
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