Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles

Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles Full article

Journal

Russian Chemical Bulletin
ISSN: 1066-5285 , E-ISSN: 1573-9171

Output data

Year: 2015, Volume: 64, Number: 3, Pages: 499-510 Pages count : DOI: 10.1007/s11172-015-0893-7

Tags

anions; donor-acceptor interactions; density functional theory; 1,2,5-chalcogenadiazoles

Authors

Semenov N. A. ¹ , Lonchakov A. V. ² , Gritsan N. P. ^2,3 , Zibarev A. V. ^1,3,4

Affiliations

1	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Novosibirsk Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, VV Voevodsky Inst Chem Kinet & Combust, Siberian Branch, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
4	(Данные Web of science) Tomsk State Univ, Dept Chem, Tomsk 634050, Russia

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.

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 OpenAlex

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

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

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

DB	Citing
Web of science	24
Scopus	24
Elibrary	22
OpenAlex	24