One-Electron Versus two-Electron Transfer Processes in the Mechanism of Oxidation-Reduction Reactions in Solution

Nature ◽  
1958 ◽  
Vol 181 (4612) ◽  
pp. 825-826 ◽  
Author(s):  
JOSEPH WEISS
Keyword(s):  
Electron Transfer ◽  
Reduction Reactions ◽  
Transfer Processes ◽  
Oxidation Reduction ◽  
Mechanism Of Oxidation ◽  
Electron Transfer Processes

On the theory of electron-transfer processes in aqueous solutions

1954 ◽  
Vol 222 (1148) ◽  
pp. 128-141 ◽  
Keyword(s):  
Electron Transfer ◽  
Point Of View ◽  
Complex Ions ◽  
Gaseous State ◽  
Biochemical Processes ◽  
Transfer Processes ◽  
Oxidation Reduction ◽  
Mechanical Interpretation ◽  
Electron Transfer Processes

It has been realized for some time that simple electron-transfer processes play an important part in the mechanism of many oxidation-reduction reactions in solution. An attempt has been made to give a quantum-mechanical interpretation of these processes on the basis of the earlier theories of electron transfer in the gaseous state (Landau 1932; Bates & Massey 1943). The present treatment for solutions takes into account the role of the solvent, with particular reference to the operation of the Franck—Condon principle and it also leads to some definite picture of the transition state for the electron transfer process. A number of examples are discussed, including electron transfer between like ions of different valency and also reactions involving complex ions, e.g. metal porphyrins, the reactions of which are of importance in certain biochemical processes. It appears that the application of certain theoretical principles leads to a satisfactory understanding of electron-transfer processes in solution from a qualitative and, in some cases, also from a semi-quantitative point of view.

Electron Transfer Processes

2006 ◽  
Author(s):  
Abraham Nitzan
Keyword(s):  
Electron Transfer ◽  
Reduction Process ◽  
Chemical Processes ◽  
Theoretical Concepts ◽  
Molecular Systems ◽  
The Core ◽  
Transfer Processes ◽  
Biological Phenomena ◽  
Oxidation Reduction ◽  
Electron Transfer Processes

Electron transfer processes are at the core of all oxidation–reduction reactions, including those associated with electrochemistry and corrosion. Photoelectrochemistry and solar energy conversion, organic light emitting diodes, and molecular electronic devices, all dominated by electron transfer and electron transmission in molecular systems, are presently subjects of intensive research at the interface of science and technology. Similarly, electron transfer processes constitute fundamental steps in important biological phenomena such as photosynthesis and vision. This chapter is an introduction to the general phenomenology and theoretical concepts associated with these processes. Electron transfer is one of the most important, and most studied, elementary chemical processes. This most fundamental oxidation–reduction process lies at the core of many chemical phenomena ranging from photosynthesis to electrochemistry and from the essential steps governing vision to the chemical processes controlling corrosion. As other molecular phenomena that involve charges and charged particles, the natural environment for such processes is a polar solution; the solvation energy associated with the polarization of the environment is a major component in the energetics of such processes. Noting that in vacuum typical molecular ionization potentials are of the order of (100–400)kBT for T = 300 K, it appears that the stabilization of ionic species by the solvent environment is the reason why electron transfer processes in solution can take place at room temperature. When we try to go beyond this general statement, questions arise.

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

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