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Donor–Acceptor Complexes between 1,2,5‐Chalcogenadiazoles (Te, Se, S) and the Pseudohalides CN − and XCN − (X=O, S, Se, Te)
Author(s) -
Semenov Nikolay A.,
Gorbunov Dmitry E.,
Shakhova Margarita V.,
Salnikov Georgy E.,
Bagryanskaya Irina Y.,
Korolev Valery V.,
Beckmann Jens,
Gritsan Nina P.,
Zibarev Andrey V.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802257
Subject(s) - chalcogen , crystallography , chemistry , acceptor , hyperconjugation , covalent bond , van der waals force , van der waals radius , molecule , organic chemistry , physics , condensed matter physics
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 ‐C 6 F 4 Hg) 3 , which was characterized by XRD.