Kinetics of dissociative electron transfer. Direct and mediated electrochemical reductive cleavage of the carbon-halogen bond

1986 ◽  
Vol 90 (16) ◽  
pp. 3815-3823 ◽  
Author(s):  
Claude P. Andrieux ◽  
Jean Michel Saveant ◽  
Khac Binh Su
Keyword(s):  
Electron Transfer ◽  
Halogen Bond ◽  
Reductive Cleavage ◽  
Dissociative Electron Transfer ◽  
Kinetics Of

Dissociative electron transfer. Homogeneous and heterogeneous reductive cleavage of the carbon-halogen bond in simple aliphatic halides

1986 ◽  
Vol 108 (4) ◽  
pp. 638-647 ◽  
Author(s):  
Claude P. Andrieux ◽  
Iluminada. Gallardo ◽  
Jean Michel. Savaent ◽  
Khac Binh. Su
Keyword(s):  
Electron Transfer ◽  
Halogen Bond ◽  
Reductive Cleavage ◽  
Dissociative Electron Transfer

Dissociative electron transfer. Ab initio study of the carbon-halogen bond reductive cleavage in methyl and perfluoromethyl halides. Role of the solvent

1992 ◽  
Vol 114 (24) ◽  
pp. 9576-9583 ◽  
Author(s):  
Juan Bertran ◽  
Iluminada Gallardo ◽  
Miquel Moreno ◽  
Jean Michel Saveant
Keyword(s):  
Electron Transfer ◽  
Ab Initio ◽  
Halogen Bond ◽  
Reductive Cleavage ◽  
Ab Initio Study ◽  
Dissociative Electron Transfer

Reductive cleavage of carbon–chlorine bonds at catalytic and non-catalytic electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate

2015 ◽  
Vol 17 (46) ◽  
pp. 31228-31236 ◽  
Author(s):  
Abdirisak A. Isse ◽  
Ludovico Scarpa ◽  
Christian Durante ◽  
Armando Gennaro
Keyword(s):  
Electron Transfer ◽  
Electrocatalytic Activity ◽  
Reductive Cleavage ◽  
Dissociative Electron Transfer ◽  
Concerted Mechanism ◽  
Good Electrocatalytic Activity

Silver shows good electrocatalytic activity for the reduction of organic chlorides only when the dissociative electron transfer follows a concerted mechanism.

Electron-transfer reactions of halogenated electrophiles: a different look into the nature of halogen bonding

2017 ◽  
Vol 203 ◽  
pp. 315-332 ◽  
Author(s):  
Sergiy V. Rosokha
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Halogen Bond ◽  
Structural Characteristics ◽  
Halogen Bonding ◽  
Outer Sphere ◽  
Ferrocene Derivatives ◽  
Dissociative Electron Transfer ◽  
Covalent Interaction ◽  
Electron Transfer Theory

The rates of oxidation of ferrocene derivatives by brominated molecules R-Br (CBr3CN, CBr4, CBr3NO2, CBr3COCBr3, CBr3CONH2, CBr3F, and CBr3H) were consistent with the predictions of the outer-sphere dissociative electron-transfer theory. The similar redox-reactions of the R-Br electrophiles with the typical halogen-bond acceptors tetramethyl-p-phenylenediamine (TMPD) or iodide were much faster than calculated using the same model. The fast redox-processes in these systems were related to the involvement of the transient halogen-bonded [R-Br, TMPD] or [R-Br, I−] complexes in which barriers for electron transfer were lowered by the strong electronic coupling of reactants. The Mulliken–Hush treatment of the spectral and structural characteristics of the [R-Br, TMPD] or [R-Br, I−] complexes corroborated the values of coupling elements, Hab, of 0.2–0.5 eV implied by the kinetic data. The Natural Bond Orbital analysis of these complexes indicated a noticeable donor/acceptor charge transfer, Δq, of 0.03–0.09 ē. The Hab and Δq values in the [R-Br, TMPD] and [R-Br, I−] complexes (which are similar to those in the traditional charge-transfer associates) indicate significant contribution of charge-transfer (weakly-covalent) interaction to halogen bonding. The decrease of the barrier for electron transfer between the halogen-bonded reactants demonstrated in the current work points out that halogen bonding should be taken into account in the mechanistic analysis of the reactions of halogenated species.

Localized TiIII mediated dissociative electron transfer for carbon halogen bond activation on TiO2

2017 ◽  
Vol 219 ◽  
pp. 322-328 ◽  
Author(s):  
Qian Zhu ◽  
Yuanyuan Wang ◽  
Hongna Zhang ◽  
Ran Duan ◽  
Chuncheng Chen ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Bond Activation ◽  
Halogen Bond ◽  
Dissociative Electron Transfer
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