Donor-Acceptor Complexes between 1,2,5-Chalcogenadiazoles (Te, Se, S) and the Pseudohalides CN- and XCN- (X=O, S, Se, Te)

Nikolay A Semenov; Dmitry E Gorbunov; Margarita V Shakhova; Georgy E Salnikov; Irina Y Bagryanskaya; Valery V Korolev; Jens Beckmann; Nina P Gritsan; Andrey V Zibarev

doi:10.1002/chem.201802257

Donor-Acceptor Complexes between 1,2,5-Chalcogenadiazoles (Te, Se, S) and the Pseudohalides CN^- and XCN^- (X=O, S, Se, Te)

Chemistry. 2018 Sep 3;24(49):12983-12991. doi: 10.1002/chem.201802257. Epub 2018 Jul 27.

Authors

Nikolay A Semenov¹, Dmitry E Gorbunov^{2

3}, Margarita V Shakhova^{2

3}, Georgy E Salnikov^{1

4}, Irina Y Bagryanskaya¹, Valery V Korolev², Jens Beckmann⁵, Nina P Gritsan^{2

3}, Andrey V Zibarev^{1

3

6}

Affiliations

¹ Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia.
² Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia.
³ Department of Physics, Novosibirsk State University, 630090, Novosibirsk, Russia.
⁴ Department of Natural Sciences, Novosibirsk State University, 630090, Novosibirsk, Russia.
⁵ Institute for Inorganic Chemistry and Crystallography, University of Bremen, 28359, Bremen, Germany.
⁶ Department of Chemistry, Tomsk State University, 643050, Tomsk, Russia.

PMID: 29882626
DOI: 10.1002/chem.201802257

Abstract

Donor-acceptor (D-A) complexes between 3,4-dicyano-1,2,5-chalcogenadiazoles [chalcogen=Te (1 a), Se (1 b), S (1 c)] and the pseudohalides CN^- and XCN^- (X=O, S, Se, Te) were studied experimentally and theoretically. For 1 a, they were isolated as [K(18-crown-6)][1 a-CN] (2), [K(18-crown-6)][1 a-NCO] (3), [K(18-crown-6)][1 a-SCN] (4), [K(18-crown-6)][1 a-SeCN] (5), and [K][1 a-NCSe] (6) and characterized by X-ray diffraction (XRD), UV/Vis and NMR spectroscopy, and DFT and QTAIM calculations. For 1 b and 1 c, the complexes were not isolated due to unfavorable thermodynamics. In all isolated complexes, the D-A bonds, stabilized by negative hyperconjugation, were longer than the sum of the covalent radii and shorter than the sum of the van der Waals radii of the bonded atoms. In mixtures of 1 a, F^- , and SeCN^- , the complex [1 a-F]^- was selectively formed in accordance with thermodynamics. The reaction of 1 a with SeCN^- and the cyclic trimeric perfluoro-ortho-phenylene mercury afforded the complex [K(18-crown-6)][SCN]⋅(o-C₆ F₄ Hg)₃ , which was characterized by XRD.

Keywords: anions; chalcogens; donor-acceptor systems; pseudohalides; receptors.