Interaction of 1,2,5-chalcogenadiazole derivatives with thiophenolate: Hypercoordination with formation of interchalcogen bond versus reduction to radical anion

Elizaveta A. Suturina, Nikolay A. Semenov, Anton V. Lonchakov, Irina Yu Bagryanskaya, Yuri V. Gatilov, Irina G. Irtegova, Nadezhda V. Vasilieva, Enno Lork, Rüdiger Mews, Nina P. Gritsan, Andrey V. Zibarev

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Abstract

According to the DFT calculations, [1,2,5]thiadiazolo[3,4-c][1,2,5] thiadiazole (4), [1,2,5]selenadiazolo[3,4-c][1,2,5]thiadiazole (5), 3,4-dicyano-1,2,5-thiadiazole (6), and 3,4-dicyano-1,2,5-selenadiazole (7) have nearly the same positive electron affinity (EA). Under the CV conditions they readily produce long-lived π-delocalized radical anions (π-RAs) characterized by EPR. Whereas 4 and 5 were chemically reduced into the π-RAs with thiophenolate (PhS-), 6 did not react and 7 formed a product of hypercoordination at the Se center (9) isolated in the form of the thermally stable salt [K(18-crown-6)][9] (10). The latter type of reactivity has never been observed previously for any 1,2,5-chalcogenadiazole derivatives. The X-ray structure of salt 10 revealed that the Se-S distance in the anion 9 (2.722 Å) is ca. 0.5 Å longer than the sum of the covalent radii of these atoms but ca. 1 Å shorter than the sum of their van der Waals radii. According to the QTAIM and NBO analysis, the Se-S bond in 9 can be considered a donor-acceptor bond whose formation leads to transfer of ca. 40% of negative charge from PhS- onto the heterocycle. For various PhS -/1,2,5-chalcogenadiazole reaction systems, thermodynamics and kinetics were theoretically studied to rationalize the interchalcogen hypercoordination vs reduction to π-RA dichotomy. It is predicted that interaction between PhS- and 3,4-dicyano-1,2,5-telluradiazole (12), whose EA slightly exceeds that of 6 and 7, will lead to hypercoordinate anion (17) with the interchalcogen Te-S bond being stronger than the Se-S bond observed in anion 9.

Original languageEnglish
Pages (from-to)4851-4860
Number of pages10
JournalJournal of Physical Chemistry A
Volume115
Issue number18
DOIs
Publication statusPublished - 12 May 2011

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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    Suturina, E. A., Semenov, N. A., Lonchakov, A. V., Bagryanskaya, I. Y., Gatilov, Y. V., Irtegova, I. G., Vasilieva, N. V., Lork, E., Mews, R., Gritsan, N. P., & Zibarev, A. V. (2011). Interaction of 1,2,5-chalcogenadiazole derivatives with thiophenolate: Hypercoordination with formation of interchalcogen bond versus reduction to radical anion. Journal of Physical Chemistry A, 115(18), 4851-4860. https://doi.org/10.1021/jp2019523