experimental values
electron transfer
differences
reagents
sphere
orders of magnitude
kinetics
diazonium
bonds
organic cations
2022-10-01T06:27
coordination sphere
account
transfer products
calculations
recombination
description
values
organic electron donors
magnitude
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.
reduction
quantum chemical calculations
tropylium cation
process
order
1987-03-01
transfer
158-163
rate constants
substantial changes
1987-03
corresponding radicals
reorganization energy
Application of the Marcus theory to description of the kinetics of reduction processes of organic cations
radicals
dissociation energies
higher values
direct electron transfer
article
tropylium
energy
electron donor
pyrylium cations
applications
donors
reduction process
theory
structure
https://doi.org/10.1007/bf00534575
outer coordination sphere
products
cations
Marcus theory
electron transfer products
changes
false
constants
inner coordination sphere
articles
https://scigraph.springernature.com/explorer/license/
allowance
equations
V. I.
Bogillo
pub.1012871655
dimensions_id
L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev
L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev
doi
10.1007/bf00534575
Physical Chemistry (incl. Structural)
Chemical Sciences
Lobanov
V. V.
0040-5760
1573-935X
Theoretical and Experimental Chemistry
Springer Nature
Gragerov
I. P.
2
Springer Nature - SN SciGraph project
23