Abstract: Synthetic, structural, and thermodynamic aspects of the recently discovered new reaction, donor-acceptor coordination of anions (A(-)) by chalcogen atoms (E) of 1,2,5-chalcogenadiazoles, are considered. According to the quantum chemical calculations, the charge transfer from A-to the heterocycle via the mechanism of negative hyperconjugation (i.e., from the MO of the lone pair of A(-) to the virtual sigma* orbital of the E-N bond of chalcogenadiazole) depends on the nature of E and A(-), being 0.42-0.52 and 0.30-0.44 e in terms of the Mulliken and NBO methods, respectively. According to the X-ray diffraction data, the E-A(-) coordinate bond is always longer than the sum of the covalent radii but shorter than the sum of the van der Waals radii of the atoms forming the bond. The E-A(-) bond energy varies in a wide range, from similar to 25 kcal mol(-1) comparable to the energy of weak covalent bonds (e.g., internal N-N bond in organic azides) to similar to 86 kcal mol(-1) comparable to the C-C bond energy in organic compounds. The quantum chemical estimations of the thermodynamics of the donor-acceptor coordination of the anions by the chalcogen atoms of 1,2,5-chalcogenadiazoles indicate that for E = Te and Se this reaction may be of general character also covering E = S in some cases.

Cite: Semenov N.A. , Lonchakov A.V. , Gritsan N.P. , Zibarev A.V.
Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles
Russian Chemical Bulletin. 2015. V.64. N3. P.499-510. DOI: 10.1007/s11172-015-0893-7 WOS Scopus РИНЦ

ArticleLinkType.TRANSLATED_TO_ORIGINAL: Семенов Н.А. , Лончаков А.В. , Грицан Н.П. , Зибарев А.В.
Донорно-акцепторная координация анионов атомами халькогенов 1,2,5-халькогенадиазолов
Известия Академии наук. Серия химическая.(RUSS CHEM B+). 2015. №3. С.499. РИНЦ

Dates:

Published print:	Mar 1, 2015
Published online:	Nov 19, 2015

Identifiers:

Web of science	WOS:000365184100002
Scopus	2-s2.0-84947552180
Elibrary	24971983
OpenAlex	W2256825265

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