Radical Anions, Radical‐Anion Salts, and Anionic Complexes of 2,1,3‐Benzochalcogenadiazoles
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В журнале Chemistry - A European Journal  Volume 25, Issue 3, January 21, 2019, Pages 806-816 (IF=5,16) опубликован статья  с участием сотрудников Института Е.А. Чулановой, д.х.н. Л.А. Шундрина, Г.Е. Сальникова, к.х.н. А.М. Генаева, к.х.н.И.Г. Иртеговой, д.х.н. И.Ю. Багрянской, д.х.н. А.В. Зибарева

 


Radical Anions, Radical‐Anion Salts, and Anionic Complexes of 2,1,3‐Benzochalcogenadiazoles

Dr. Nikolay A. Pushkarevsky,  Elena A. Chulanova,  Prof. Dr. Leonid A. Shundrin,  Dr. Anton I. Smolentsev,  Dr. Georgy E. Salnikov,  Dr. Elena A. Pritchina,  Dr. Alexander M. Genaev,  Dr. Irina G. Irtegova, Prof. Dr. Irina Yu. Bagryanskaya,  Prof. Dr. Sergey N. Konchenko,  Prof. Dr. Nina P. Gritsan,  Prof. Dr. Jens Beckmann,  Prof. Dr. Andrey V. Zibarev



Volume25, Issue3January 14, 2019, Pages 806-816
First online: 15 January 2019



 https://doi.org/10.1002/chem.201803465


Abstract

By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron‐acceptor ability of 2,1,3‐benzochalcogenadiazoles 13 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [1].− and [2].−, RA [3].− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 13 was performed and new thermally stable RA salts [K(THF)]+[2].− (8) and [K(18‐crown‐6)]+[2].− (9) were isolated in addition to known salt [K(THF)]+[1].− (7). On contact with air, RAs [1].− and [2].−underwent fast decomposition in solution with the formation of anions [ECN], which were isolated in the form of salts [K(18‐crown‐6)]+[ECN] (10, E=S; 11, E=Se). In the case of3, RA [3].− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π‐heterocyclic RAs but not isolated. Instead, salt [K(18‐crown‐6)]+2[3‐Te2]2− (12) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18‐crown‐6)]+2[3‐Te43]2− (13) containing an anionic complex with two coordinate Te−Te bonds. The structures of 813 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [3‐Te2]2− and [3‐Te43]2− was studied by DFT calculations and QTAIM analysis.

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