J. Matsui, Hyun Park, K. Otsuka
Oct 30, 2003
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Influential Citations
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Journal
Journal of Electroanalytical Chemistry
Abstract
Abstract The reactions of 9-substituted anthracene cation radicals (XA+ s) with water and methanol in acetonitrile were analyzed using an electron transfer stopped-flow (ETSF) method. By adopting the tris(2,4-dibromophenyl)amine cation radical (TDBPA+ ) as a reaction initiator, five XA+ s, i.e. phenyl, bromo, acetyl, benzyl, and methyl derivatives, could be generated quantitatively by mixing XA with TDBPA+ , and the chemical reaction processes of XA+ s with water or methanol (ROH) could then be followed by observing dynamic transformation processes of the absorption spectra. Consequently, the reaction orders of XA+ and ROH as well as the reaction rates could be determined. The order of the reactivity was anthracene+ >9-methylanthracene+ >9-benzylanthracene+ >9-acetylanthracene+ , 9-bromoanthracene+ >9-phenylanthracene+ , and diverse changes in the reaction orders of both XA+ and ROH were observed indicating some mechanistic changes. The order of the reactivity was difficult to explain only on the basis of the character of XAs or XA+ s. However, as a hypothesis, it can be assumed that when the electron transfer between XA+ and XA(ROH)+ is favorable to formation of XA(ROH)2+, the reaction order of [XA+ ] is second, and the reaction rates become faster.