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Molecules 2014, 19(8), 11999-12010; https://doi.org/10.3390/molecules190811999

Dissociative Electron Transfer to Diphenyl-Substituted Bicyclic Endoperoxides: The Effect of Molecular Structure on the Reactivity of Distonic Radical Anions and Determination of Thermochemical Parameters

1
Department of Chemistry, University of Malta, Msida, MSD 2080, Malta
2
Department of Chemistry, The University of Western Ontario, London, ON N6A 5B7, Canada
*
Authors to whom correspondence should be addressed.
Received: 24 June 2014 / Revised: 29 July 2014 / Accepted: 1 August 2014 / Published: 11 August 2014
(This article belongs to the Special Issue Free Radicals and Radical Ions)
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Abstract

The heterogeneous electron transfer reduction of the bicyclic endoperoxide 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]hept-5-ene (4) was investigated in N,N-dimethylformamide at a glassy carbon electrode. The endoperoxide reacts by a concerted dissociative ET mechanism resulting in reduction of the O-O bond with an observed peak potential of −1.4 V at 0.2 V s−1. The major product (90% yield) resulting from the heterogeneous bulk electrolysis of 4 at −1.4 V with a rotating disk glassy carbon electrode is 1,4-diphenyl-cyclopent-2-ene-cis-1,3-diol with a consumption of 1.73 electrons per mole. In contrast, 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (1), undergoes a two-electron reduction mechanism in quantitative yield. This difference in product yield between 1 and 4 is suggestive of a radical-anion mechanism, as observed with 1,4-diphenyl-2,3-dioxabicyclo-[2.2.2] octane (2) and 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]heptane (3). Convolution potential sweep voltammetry is used to determine unknown thermochemical parameters of 4, including the O-O bond dissociation energy and the standard reduction potential and a comparison is made to the previously studied bicyclic endoperoxides 13 with respect to the effect of molecular structure on the reactivity of distonic radical anions. View Full-Text
Keywords: dissociative electron transfer; distonic radical ion; endoperoxide; convolution analysis; electrode interface; cyclic voltammetry dissociative electron transfer; distonic radical ion; endoperoxide; convolution analysis; electrode interface; cyclic voltammetry
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Magri, D.C.; Workentin, M.S. Dissociative Electron Transfer to Diphenyl-Substituted Bicyclic Endoperoxides: The Effect of Molecular Structure on the Reactivity of Distonic Radical Anions and Determination of Thermochemical Parameters. Molecules 2014, 19, 11999-12010.

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