Kinetics of the reduction of organic cations by cation radicals View Full Text


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Article Info

DATE

1985-01

AUTHORS

V. I. Bogillo, I. P. Gragerov

ABSTRACT

It has been found that the reduction of substituted diazonium, iodonium, and tropylium salts by cation radicals of tetra-tert-butyl-bis-pyrylium, tetramethyl-p-phenylene diamine (I), tetraphenylbenzidine, and N-methylphenothiazine obey the kinetic equation of the second order and that it follows an electron transfer mechanism. The logarithms of the rate constants of these reactions decrease with increasing standard free energy of the electron transfer reaction. The rate of the reaction of C6H5N2+ BF4− with I and the selectivity of the reactions of the substituted diazonium salts with I increases with the electron donor capacity of the solvent. The addition of crown-ethers accelerates the reaction. The reaction rate increases also with increasing ionic strength of the solution, whereby the Cl− anions have a specifically accelerating effect. The observed rules governing the influence of the medium contradict those found earlier for the interaction of organic cations with neutral radicals and anion radicals. This is attributed to the fact that the electron transfer takes place in ternary complexes cation-solvent (crown ether, Cl− ion)-cation radical. More... »

PAGES

42-48

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Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf00524309

DOI

http://dx.doi.org/10.1007/bf00524309

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1049867046


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