Research output: Contribution to journal › Article › peer-review
Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles. / Semenov, N. A.; Lonchakov, A. V.; Gritsan, N. P. et al.
In: Russian Chemical Bulletin, Vol. 64, No. 3, 01.03.2015, p. 499-510.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles
AU - Semenov, N. A.
AU - Lonchakov, A. V.
AU - Gritsan, N. P.
AU - Zibarev, A. V.
PY - 2015/3/1
Y1 - 2015/3/1
N2 - 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 σorbital 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 ~25 kcal mol-1 comparable to the energy of weak covalent bonds (e.g., internal N - N bond in organic azides) 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.
AB - 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 σorbital 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 ~25 kcal mol-1 comparable to the energy of weak covalent bonds (e.g., internal N - N bond in organic azides) 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.
KW - 1,2,5-chalcogenadiazoles
KW - anions
KW - density functional theory
KW - donor-acceptor interactions
UR - http://www.scopus.com/inward/record.url?scp=84947552180&partnerID=8YFLogxK
U2 - 10.1007/s11172-015-0893-7
DO - 10.1007/s11172-015-0893-7
M3 - Article
AN - SCOPUS:84947552180
VL - 64
SP - 499
EP - 510
JO - Russian Chemical Bulletin
JF - Russian Chemical Bulletin
SN - 1066-5285
IS - 3
ER -
ID: 25832798