Application of the Marcus theory to description of the kinetics of reduction processes of organic cations
The calculation of the rate constants for the processes in the reduction of diazonium, tropylium, verdazylium, and pyrylium cations by various organic electron donors, using the equations of the Marcus theory with allowance for the reorganization energy of only the outer coordination sphere, leads to values which are one to seven orders of magnitude higher than the experimental values. By quantum-chemical calculations it was shown that the reduction of diazonium and tropylium cations to the corresponding radicals is accompanied by a substantial change in the structure of the reagents. This leads to high values for the reorganization energy of the inner coordination sphere of the cations, which must be taken into account during calculation of the rate constants. The differences in the rate constants of the processes of direct electron transfer from the electron donors to the organic cations and the recombination of these reagents depend on the dissociation energy of the bond of the cation with the donor leading to the electron transfer products.
- Research Organization:
- L. V. Pisarzhevskii Institute of Physical Chemistry, USSR
- OSTI ID:
- 5889589
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Vol. 23:2; Other Information: Translated from Teor. Eksp. Khim.; 23: No. 2, 167-172(Mar-Apr 1987)
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ORGANIC COMPOUNDS
ATOMIC MODELS
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
REDUCTION
VALENCE
ACETIC ACID
AMIDES
AMINES
CATIONS
CHEMICAL REACTION KINETICS
DISSOCIATION ENERGY
POLYATOMIC MOLECULES
QUANTUM MECHANICS
QUINONES
RADICALS
REDOX POTENTIAL
STEREOCHEMISTRY
WAVE FUNCTIONS
AROMATICS
CARBOXYLIC ACIDS
CHARGED PARTICLES
CHEMICAL REACTIONS
ENERGY
FUNCTIONS
IONS
KINETICS
MATHEMATICAL MODELS
MECHANICS
MOLECULES
MONOCARBOXYLIC ACIDS
ORGANIC ACIDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION KINETICS
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory