Interaction of 1,2,5-Chalcogenadiazole Derivatives with Thiophenolate: Hypercoordination with Formation of Interchalcogen Bond versus Reduction to Radical Anion

Interaction of 1,2,5-Chalcogenadiazole Derivatives with Thiophenolate: Hypercoordination with Formation of Interchalcogen Bond versus Reduction to Radical Anion Full article

Journal

Journal of Physical Chemistry A
ISSN: 1089-5639

Output data

Year: 2011, Volume: 115, Number: 18, Pages: 4851-4860 Pages count : DOI: 10.1021/jp2019523

Authors

Suturina Elizaveta A. ^2,3 , Semenov Nikolay A. ⁴ , Lonchakov Anton V. ^2,3 , Bagryanskaya Irina Yu. ⁴ , Gatilov Yuri V. ⁴ , Irtegova Irina G. ⁴ , Vasilieva Nadezhda V. ⁴ , Lork Enno ¹ , Mews Ruediger ¹ , Gritsan Nina P. ^2,3 , Zibarev Andrey V. ^3,4

Affiliations

1	(Данные Web of science) Univ Bremen, Inst Inorgan & Phys Chem, D-28334 Bremen, Germany
2	(Данные Web of science) Russian Acad Sci, Siberian Branch, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Phys, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, Inst Organ Chem, Novosibirsk 630090, Russia

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 (FA). Under the CV conditions they readily produce long-lived pi-delocalized radical anions (pi-RAs) characterized by EPR. Whereas 4 and 5 were chemically reduced into the pi-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 angstrom) is ca. 0.5 angstrom longer than the sum of the covalent radii of these atoms but ca. 1 angstrom 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 pi-RA dichotomy. It is predicted that interaction between PhS- and 3,4-clicyano-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.

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.
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. 2011. V.115. N18. P.4851-4860. DOI: 10.1021/jp2019523 WOS Scopus

Published print:

May 12, 2011

Web of science	WOS:000290126900033
Scopus	2-s2.0-79955788099
OpenAlex	W2332377841