Abstract
The kinetics of photoinduced reduction of a series of 3,5- and 3,6-di-tert-butylbenzoquinones-1,2 was studied in the presence of N,N-dimethylaniline, its deuterated analog, and a series of para-substituted N, N-dimethylanilines. On passing from the endothermic to the exothermic range of the free energy of electron transfer ΔG e , the effective rate constants k H and k D and the quantum yields ϕH and ϕD of the reaction varied nonmonotonically with a maximum at ΔG e of approximately +0.1 eV. For the reactant pairs relevant to the ascending (left-hand) branch of the plot k H = f(ΔG e ), the H/D isotope effect takes place, varying from two to five in magnitude. For the reactant pairs at the maximum and in the descending (right-hand) branch of the plot k H = f(ΔG e ), there is no isotope effect or its value is insignificant.
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Translated from Khimiya Vysokikh Energii, Vol. 39, No. 5, 2005, pp. 348–352.
Original Russian Text Copyright © 2005 by Abakumov, Shurygina, Chesnokov, Druzhkov, Lopatin, Chechet, Cherkasov.
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Abakumov, G.A., Shurygina, M.P., Chesnokov, S.A. et al. Kinetic Isotope Effect in the Photoreduction of o-Benzoquinones in the Presence of N,N-Dimethylaniline. High Energy Chem 39, 299–303 (2005). https://doi.org/10.1007/s10733-005-0059-5
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DOI: https://doi.org/10.1007/s10733-005-0059-5