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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Interaction of 1,2,5-chalcogenadiazole derivatives with thiophenolate: Hypercoordination with formation of interchalcogen bond versus reduction to radical anion
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Interaction of 1,2,5-chalcogenadiazole derivatives with thiophenolate: Hypercoordination with formation of interchalcogen bond versus reduction to radical anion

机译：1,2,5-硫族二唑衍生物与硫酚酸酯的相互作用：硫族键形成与形成自由基阴离子的过度配位

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摘要

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 ?) is ca. 0.5 ? longer than the sum of the covalent radii of these atoms but ca. 1 ? 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.
机译：根据DFT计算，[1,2,5]噻二唑[3,4-c] [1,2,5]噻二唑（4），[1,2,5] selenadiazolo [3,4-c] [1 ，2,5]噻二唑（5），3,4-二氰基-1,2,5-噻二唑（6）和3,4-二氰基-1,2,5-硒代二唑（7）具有几乎相同的正电子亲和力（EA）。在CV条件下，它们容易产生以EPR为特征的长寿命π-离域自由基阴离子（π-RAs）。而4和5被硫酚盐（PhS-）化学还原成π-RAs，6不反应，7在Se中心形成超配位产物（9），以热稳定盐的形式分离[K（18 -crown-6）] [9]（10）。以前从未对任何1,2,5-硫属二唑衍生物观察到后者的反应性。盐10的X射线结构表明，阴离子9中的Se-S距离约为2.722Ω。 0.5？比这些原子的共价半径之和长，但是大约1个短于范德华半径之和。根据QTAIM和NBO分析，可以将9中的Se-S键视为供体-受体键，其形成导致ca的转移。从PhS-到杂环的负电荷的40％。对于各种PhS-/ 1,2,5-硫族二唑反应体系，从理论上研究了热力学和动力学，以合理地解释硫族间超配合与还原成π-RA二分法的关系。据预测，PhS-和3,4-二氰基-1,2,5-telluradiazole（12）之间的相互作用（其EA稍微超过6和7的EA）将与硫族间生Te-S产生超配位阴离子（17）。键比阴离子9中观察到的Se-S键强。

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