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On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-3832-2331
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-2673-075X
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2017 (English)In: CHEMELECTROCHEM, ISSN 2196-0216, Vol. 4, no 12, p. 3212-3221Article in journal (Refereed) Published
Abstract [en]

In this work, sampled-current voltammetry performed on a series of aryldiazonium, diaryliodonium, and triarylsulfonium salts allows the determination of the reduction potential of aryl radicals in acetonitrile. Specifically, this is accomplished by measuring the number of electrons consumed in the reduction process as a function of the applied potential. For the phenyl, 4-bromophenyl, and 4-nitrophenyl radicals, the reduction potential is found to be -0.91 +/- 0.06, -0.90 +/- 0.10, and -0.98 +/- 0.06 V vs. SCE, respectively. Furthermore, from measurements on an extended series of substituted compounds, it is concluded that the substituent effect on the reduction potential is small, which can be explained by the sigma nature of the aryl radical as evidenced from theoretical calculations. At the same time this yields a mean value for the reduction potential of the aryl radical of -0.87 V +/- 0.03 V vs. SCE. Determination of the intrinsic barrier and the standard potential from the data obtained are more uncertain since it is unknown to which extent the competing reference reaction, the electrochemical grafting reaction, is affected by the applied potential. From calculations using density functional theory, the intrinsic barrier for the reduction of the phenyl radical is determined to be 0.32 eV.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH , 2017. Vol. 4, no 12, p. 3212-3221
Keywords [en]
aryldiazonium salts, density functional calculations, phenyl radicals, reduction potential, sampled-current voltammetry
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Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-221876DOI: 10.1002/celc.201700772ISI: 000419269000025Scopus ID: 2-s2.0-85032256466OAI: oai:DiVA.org:kth-221876DiVA, id: diva2:1178738
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QC 20180130

Available from: 2018-01-30 Created: 2018-01-30 Last updated: 2018-01-30Bibliographically approved

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Halldin Stenlid, JoakimBrinck, Tore

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