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





2015 ◽  
Vol 17 (46) ◽  
pp. 31228-31236 ◽  
Author(s):  
Abdirisak A. Isse ◽  
Ludovico Scarpa ◽  
Christian Durante ◽  
Armando Gennaro

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



2017 ◽  
Vol 203 ◽  
pp. 315-332 ◽  
Author(s):  
Sergiy V. Rosokha

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.



2017 ◽  
Vol 219 ◽  
pp. 322-328 ◽  
Author(s):  
Qian Zhu ◽  
Yuanyuan Wang ◽  
Hongna Zhang ◽  
Ran Duan ◽  
Chuncheng Chen ◽  
...  




1998 ◽  
Vol 34 (2) ◽  
pp. 57-68 ◽  
Author(s):  
Yurii A. Maletin ◽  
Roderick D. Cannon


Sign in / Sign up

Export Citation Format

Share Document