Abstract
Nonempirical quantum-chemical calculations of pyridine and its 2-, 3-, and 4-X-substituted derivatives (X = F, Cl, Br, Me, and Et) by RHF/6-311G(d) and MP2/6-311G(d) methods indicate an alternation of charges on the atoms of the pyridine ring and of the occupancy of their valence py-orbitals. This is caused by the polarization of bonds under the action of the charges of the atoms geminal to C(n). Bonding molecular orbitals in these molecules, formed as a result of the py-orbitals, occurring in the plane of the pyridine ring, are not an indication (characteristic) of p, π-conjugation between the unshared electron pair of the heteroatom of a substituent X and the π-electron system of the ring. The results of the calculations by these methods did not differ in principle.
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Dedicated to Academician of the Russian Academy of Sciences M. G. Voronkov in honor of his 85th birthday.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1671–1681, November, 2006.
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Feshin, V.P., Feshina, E.V. & Zhizhina, L.I. Interaction of the atoms in molecules of pyridine and its derivatives according to the results of ab initio calculations. Chem Heterocycl Compd 42, 1435–1443 (2006). https://doi.org/10.1007/s10593-006-0260-6
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DOI: https://doi.org/10.1007/s10593-006-0260-6