Electrochemical behavior of α1/α2-[Fe(H2O)P2W17O61](7-) isomers in solution: experimental and DFT studies

Inorganic Chemistry
Neus VilàIsrael M Mbomekalle

Abstract

The unusual redox behavior displayed by the two isomers of the Wells-Dawson phosphotungstate anion [Fe(H(2)O)P(2)W(17)O(61)](7-) is presented. The electrochemical measurements have been performed in aqueous media at different pH values from 0.5 up to 8.0. The cyclic voltammetry has also been carried out in organic media to get additional experimental data to establish the effect of the protonation on the redox properties of both isomers. At high pH values (pH ≥ 6) or in an organic medium, the reduction of the Fe center is easier in the case of the alpha-1 isomer, whereas for the alpha-2 isomer such reduction takes place at more negative potentials, as expected. In contrast, at lower pH values (pH ≤ 5), an inversion of this trend is observed, and the reduction of the Fe center becomes easier for the alpha-2 isomer compared to the alpha-1. We were able to highlight the influence of the pH and the pK(a) of the electrolyte on POM-based redox potentials given the pK(a) of the latter. A complementary theoretical study has also been performed to explain the experimental data obtained. In this sense, the results obtained from the DFT study are in good agreement with the experimental data mentioned above and have provided additional inf...Continue Reading

References

Feb 20, 2002·Chemical Reviews·I. A. Weinstock
Feb 20, 2002·Chemical Reviews·Masahiro Sadakane, Eberhard Steckhan
Oct 17, 2002·Journal of the American Chemical Society·Xavier LópezJosep M Poblet
Jun 6, 2008·Journal of the American Chemical Society·Likai YanJosep M Poblet
Mar 5, 2010·Physical Chemistry Chemical Physics : PCCP·Coen de GraafJosep M Poblet
Jul 1, 2010·Inorganic Chemistry·Israël-Martyr MbomekalléLouis Nadjo

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Citations

Oct 22, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·N V IzarovaP Kögerler
Jul 25, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Masooma IbrahimChristopher E Anson
Feb 15, 2014·Chemical Communications : Chem Comm·Yan-Qing JiaoZhong-Min Su
Jul 15, 2021·Chemical Science·Khalid AzmaniJosé-Ramón Galán-Mascarós
Jun 13, 2015·Inorganic Chemistry·Masooma IbrahimUlrich Kortz

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