期刊
MOLECULES
卷 19, 期 8, 页码 11999-12010出版社
MDPI AG
DOI: 10.3390/molecules190811999
关键词
dissociative electron transfer; distonic radical ion; endoperoxide; convolution analysis; electrode interface; cyclic voltammetry
资金
- Natural Sciences and Engineering Research Council of Canada
- Government of Ontario (PREA)
- University of Western Ontario
- Ontario Government
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 1-3 with respect to the effect of molecular structure on the reactivity of distonic radical anions.
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