Specific deuterium isotope effects on the rates of electron transfer within geminate radical-ion pairs

The results of the first systematic study of the effect of isotopic substitution on the rates of electron transfer for reactions in the inverted region are reported. Rates of return electron transfer within germinate radical ion pairs of 9,10-dicyanoanthracene (DCA) and 2,6,9,10-tetracyanoanthracene...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1988-11, Vol.110 (23), p.7883-7885
Main Authors: Gould, Ian R., Farid, Samir
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
400202 - Isotope Effects, Isotope Exchange, & Isotope Separation
ANTHRACENE
AROMATICS
CONDENSED AROMATICS
CYANOGEN
DEUTERIUM
ELECTRON TRANSFER
HYDROCARBONS
HYDROGEN ISOTOPES
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
STABLE ISOTOPES
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Summary:The results of the first systematic study of the effect of isotopic substitution on the rates of electron transfer for reactions in the inverted region are reported. Rates of return electron transfer within germinate radical ion pairs of 9,10-dicyanoanthracene (DCA) and 2,6,9,10-tetracyanoanthracene (TCA) radical ions and radical cations of perdeuteriated methyl-substituted benzene derivatives determined by a previously reported method are tabulated. The free energies of the electron-transfer reactions for both sets of ion pairs have been calculated, and in each case the reactions with deuterated cations was slower than with undeuterated radical cations. 1 fig., 2 tabs.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00231a053