Two-electron transfer for Tl(aq)(3+)/Tl(aq)(+) revisited. Common virtual [Tl(II)-Tl(II)](4+) intermediate for homogeneous (superexchange) and electrode (sequential) mechanisms

Inorganic Chemistry
Dimitri E KhoshtariyaJulius Glaser

Abstract

Homogeneous and electrochemical two-electron transfers within the Tl(aq)(3+)/Tl(aq)(+) couple are considered on a common conceptual basis. For the 2 equiv electrochemical reduction of Tl(aq)(3+) to Tl(aq)(+), the intermediate state with a formal reduction potential, E(1) = 1.04 +/- 0.10 V vs the normal hydrogen electrode, was detected, different from the established value of 0.33 V for a Tl(3+)/Tl(2+) couple. Examination of obtained electrochemical (cyclic voltammetry (CV) and rotating disk electrode techniques, along with the CV-curve computer simulation procedure) and literature data indicate that the detected formal potential cannot be the property of electrode-adsorbed species, but rather of the covalently interacting dithallium intermediate [Tl(II)-Tl(II)](4+) located at the outer Helmholtz plane. The analysis of microscopic mechanisms, based on the recent hypothesis of H. Taube and the Marcus-Hush theory extended by Zusman and Beratan, and Koper and Schmickler, revealed that the homogeneous process most probably takes place through the superexchange inner-sphere two-electron-transfer mechanism, via an essentially virtual (undetectable) dithallium intermediate. In contrast, the electrochemical process occurs through a sequ...Continue Reading

References

Aug 1, 1971·Proceedings of the National Academy of Sciences of the United States of America·M I Page, W P Jencks
Oct 24, 2001·Inorganic Chemistry·Mikhail MaliarikImre Tóth

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Citations

Jan 15, 2015·The Journal of Physical Chemistry. B·Jiaxing LinDavid N Beratan
Apr 13, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Brendan P MacphersonRudi van Eldik
Mar 22, 2014·Nature Chemistry·Andrey V ProtchenkoSimon Aldridge
Nov 8, 2005·Inorganic Chemistry·Daniel RobertsonNikolay Gerasimchuk

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