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1.
V. B. Kobychev N. M. Vitkovskaya I. L. Zaitseva B. A. Trofimov 《Journal of Structural Chemistry》2004,45(6):940-944
The profiles of reactions leading to pyrrole anion N-adducts with CO2 and CS2 have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO2 does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004. 相似文献
2.
N. M. Vitkovskaya V. B. Kobychev E. Yu. Larionova B. A. Trofimov 《Russian Chemical Bulletin》1999,48(1):35-41
The pathways of migration of the multiple bond in propene and propyne molecules involving the hydroxide ion were investigated
by theab initio (RHF/6-31+G* and MP2/6-31+G*) methods. Stationary points corresponding to stable complexes between the molecules under study and the hydroxide ion and
between corresponding carbanions and water molecule were found on the potential energy surfaces of the proton transfer reactions.
In the presence of hydroxide ion, migration of the multiple bond can occur by an “intramolecular” mechanism of the proton
transfer involving the proton of hydroxide ion bound in the complex with propene or propyne molecule. For the propene system,
such a mechanism seems to be quite realistic and more preferable energetically than a traditional two-stage mechanism with
a passage of the proton into the medium. For the system with the triple bond, an equal expenditure of energy is required to
follow any mechanism (without taking into account the effects of solvation and the interaction with a cation), whereas the
formation of the stable [H2C=C=CH·H2O]− complex can prevent further transformations.
For Part 1, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–41, January, 1999. 相似文献
3.
N. M. Vitkovskaya V. B. Kobychev E. Yu. Larionova I. L. Zaitseva B. A. Trofimov 《Journal of Structural Chemistry》2009,50(1):18-26
Within the ab initio approach and with the use of density functional theory the formation of solvation shells of nondissociated alkali metals hydroxides of the corresponding cations and the hydroxide ion in dimethyl sulfoxide (DMSO) is studied. Complexes in which the alkali metal environment contains the coordinated acetylene molecule along with solvent molecules are considered. The coordination number of the hydroxide ion in DMSO is shown to be 4. It is demonstrated that solvated cations of alkali metals cannot form π-complexes with the acetylene molecule, whereas the introduction of molecular acetylene into the solvation sphere of nondissociated NaOH and KOH is possible. 相似文献
4.
E. Yu. Larionova N. M. Vitkovskaya V. B. Kobychev N. V. Kaempf A. D. Skitnevskaya B. A. Trofimov 《Journal of Structural Chemistry》2009,50(1):27-33
The reaction mechanism of the formation of alkali metal ethynides C2H2 + MOH → C2HM + H2O (M = Li, Na, K) is studied for the gas phase (MP2/6-311++G**//RHF/6-31+G*) and also with regard to the solvent effect of dimethyl sulfoxide (DMSO) included within the continuum model. Among all acetylene complexes with alkali metal hydroxides considered (C2H2·MOH (M = Li, Na, K)), only the complex with KOH is thermodynamically stable in DMSO solution. The formation of this structure results in activation of the acetylene molecule towards electrophilic attack. The formation of alkali metal ethynide in solution is also thermodynamically favorable only in the system with potassium hydroxide of a whole series of metals considered. Further, the ethynide ion can interact in KCCK·HOH systems. 相似文献
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6.
V. B. Kobychev N. M. Vitkovskaya N. S. Klyba B. A. Trofimov 《Journal of Structural Chemistry》2004,45(1):5-11
Ab initio (MP4/6-31G*//RHF/6-31+G*) calculations have been performed to study the acetylene–allene rearrangement in X–CH2–CCH propargyl systems, where X = ethenyl, E-1-butadienyl, 2-pyrrolyl, 2-furanyl, and 2-thienyl. The spatial and electronic structures, as well as the relative stability, of the initial and final acetylene structures and the corresponding allenes are examined. Migration of the triple bond from the terminal position into the chain, including the stage of allene structure formation, is shown to be thermodynamically favorable for the whole series of compounds. The propargyl substituents of heterocycles isomerize as readily as open diene systems. The differences in the isomerization energies in the series of allenyl- and 1-propynyl-substituted pyrrole, furan, and thiophene are mainly due to the differences in the nature of long-range interactions between heteroatoms and the tricarbon system. 相似文献
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V. B. Kobychev N. M. Vitkovskaya E. Yu. Larionova N. S. Klyba B. A. Trofimov 《Russian Chemical Bulletin》2000,49(3):408-414
Ab initio study of the pathways of migration of the double bond in the 3-methylthioprop-1-ene (1) and 3-methoxyprop-1-ene (2) molecules with participation of hydroxide ion was carried out by the RHF/6-31+G* and MP2/6-31+G//RHF/6-31+G* methods. Conformational isomerism of the initial molecules and reaction products was considered. The distinctions are discussed
in the spatial and electronic structure of intermediate carbanions stabilized (for1) due to the negative hyperconjugation. Stationary points corresponding to complexes between the molecules under study and
the hydroxide ion and between the corresponding carbanion and water molecule were localized on the potential energy surfaces
of the proton transfer reactions. For2, the single-stage mechanism of prototropic rearrangement involving the H atom of the hydroxide ions was found to be more
energetically preferable than the two-stage mechanism, whereas both mechanisms are expected to be equiprobable for1.
For Parts 1–3, see Refs. 1–3.
Translated fromIzvestiya Akademii Nauk. Seriya Kimicheskaya, No. 3, pp. 407–413, March, 2000. 相似文献
9.
F. A. Danevich A. Sh. Georgadze J. Hellmig M. Hirsch H. V. Klapdor-Kleingrothaus V. V. Kobychev B. N. Kropivyansky V. N. Kuts A. Müller A. S. Nikolaiko F. Petry O. A. Ponkratenko H. Strecker V. I. Tretyak M. Völlinger Yu. Zdesenko 《Zeitschrift für Physik A Hadrons and Nuclei》1976,355(4):433-437
A low background scintillation detector with a CdWO4 crystal of 1.046 kg was used to search for β+β+ and β+/EC processes in 106Cd. For the neutrinoless mode the limits T1/2(0νβ+β+) ≥ 2.2 · 1019 y and T1/2(0νβ+/EC) ≥ 5.5 · 1019 y were obtained with 90% C.L. For the possible two neutrino decay limits of T1/2(2νβ+β+) ≥ 9.2 · 1017 y and 1/2(2νβ+/EC) ≥ 2.6 · 1017 y have been determined with 99% C.L. 相似文献
10.
Marina Yu. Dvorko Elena Yu. Schmidt Tatyana E. Glotova Dmitrii A. Shabalin Igor' A. Ushakov Vladimir B. Kobychev Konstantin B. Petrushenko Al'bina I. Mikhaleva Boris A. Trofimov 《Tetrahedron》2012,68(7):1963-1971
A novel family of nitrogen stilbene analogs, 1-styrylpyrroles, has been synthesized in good to excellent yields by a straightforward facile transition metal-free addition of pyrroles to arylacetylenes in the KOH/DMSO system (90–120 °C, 5–13 h). Thermodynamically controlled E/Z-isomer ratio of 1-styrylpyrroles depends on structure of both pyrroles and acetylenes ranging from ca. 100% E-stereoselectivity (for the pair unsubstituted pyrrole—phenylacetylene) to 90, 96% Z-stereoselectivity (for the pairs: 2-phenylpyrrole—phenylacetylene and 2-(2-thienyl)pyrrole—phenylacetylene, respectively). 相似文献