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

Radical Anions, Radical-Anion Salts, and Anionic Complexes of 2,1,3-Benzochalcogenadiazoles Научная публикация

Журнал

Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Вых. Данные

Год: 2019, Том: 25, Номер: 3, Страницы: 806-816 Страниц : 11 DOI: 10.1002/chem.201803465

Ключевые слова

chalcogens; density functional calculations; heterocycles; main group elements; radical ions

Авторы

Pushkarevsky Nikolay A. ^1,2 , Chulanova Elena A. ^2,3 , Shundrin Leonid A. ^2,3 , Smolentsev Anton I. ¹ , Salnikov Georgy E. ^2,3 , Pritchina Elena A. ^2,4 , Genaev Alexander M. ³ , Irtegova Irina G. ³ , Bagryanskaya Irina Yu. ^2,3 , Konchenko Sergey N. ^1,2,5 , Gritsan Nina P. ^4,5 , Beckmann Jens ⁶ , Zibarev Andrey V. ^3,5,7

Организации

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, Inst Inorgan Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
5	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
6	(Данные Web of science) Univ Bremen, Inst Inorgan Chem & Crystallog, D-28359 Bremen, Germany
7	(Данные Web of science) Tomsk State Univ, Dept Chem, Tomsk 634050, Russia

By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron-acceptor ability of 2,1,3-benzochalcogenadiazoles 1-3 (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 1-3 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 of 3, RA [3](.-) was detected by EPR spectroscopy as the first representative of tellurium-nitrogen pi-heterocyclic RAs but not isolated. Instead, salt [K(18-crown-6)](+)(2)[3-Te-2](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-Te-4-3](2-) (13) containing an anionic complex with two coordinate Te-Te bonds. The structures of 8-13 were confirmed by XRD, and the nature of the Te-Te coordinate bond in [3-Te-2](2-) and [3-Te-4-3](2-) was studied by DFT calculations and QTAIM analysis.

Pushkarevsky N.A. , Chulanova E.A. , Shundrin L.A. , Smolentsev A.I. , Salnikov G.E. , Pritchina E.A. , Genaev A.M. , Irtegova I.G. , Bagryanskaya I.Y. , Konchenko S.N. , Gritsan N.P. , Beckmann J. , Zibarev A.V.
Radical Anions, Radical-Anion Salts, and Anionic Complexes of 2,1,3-Benzochalcogenadiazoles
Chemistry - A European Journal. 2019. V.25. N3. P.806-816. DOI: 10.1002/chem.201803465 WOS Scopus РИНЦ

Опубликована online:	11 дек. 2018 г.
Опубликована в печати:	14 янв. 2019 г.

Web of science	WOS:000456280800020
Scopus	2-s2.0-85056209828
РИНЦ	38631383
OpenAlex	W2886546351