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31.
Ab initio studies (LCAO-MO method) on conformers of three seleno derivatives of the biuret molecules diselenobiuret [I], selenobiuret [II], and selenothiobiuret [III] were carried out at the Hartree-Fock (HF) and MP2 levels. The molecular geometries of these species were fully optimized at the HF level and characterized by analysis of the harmonic vibrational frequencies using a split-valence triple-zeta basis set augmented by a set ofd polarization functions on heavy atoms andp polarization functions on hydrogen atoms [TZP(d, p)]. The total energies of the HF-optimized structures were calculated at the MP2 (frozen core) level using a larger TZP (2df, 2pd) basis set. The potential energy searches revealed a total of 11 minimum-energy conformers (assigned astrans-trans, trans-cis, cis-trans, andcis-cis) and seven transition-state species for the title molecules. The two predicted conformers for diselenobiuret (Ia=trans-trans andIc=cis-cis) are characterized byC 2 and the third byC s symmetry. For selenothiobiuret two forms (IIIa=trans-trans andIIId=cis-cis) possessC 1 and two (IIIb=trans-cis andIIIc=cis-trans) possessC s symmetries, respectively. For selenobiuret, four formsIIa=trans-trans (C1),IIb=trans-cis (C s),IIc=cis-trans (C 1), andIId=cis-cis (C1), were obtained as a result of gradient optimization. Comparison of the relative energies for the considered species indicated that thecis-trans forms are the most stable conformations for all three systems at both the HF and MP2 levels of theory.  相似文献   
32.
The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.  相似文献   
33.
34.
A new variational principle based on the affine connection in space-time is proposed. This leads to a new formulation of general relativity. The gravitational field is a field of inertial frames in space-time. The metricg appears as a momentum canonically conjugate to the gravitational field. In the case of simple matter fields, e.g., scalar fields, electromagnetic fields, Proca fields, or hydrodynamical matter, the new formulation is equivalent to the traditional one. A new formulation of conservation laws is proposed.  相似文献   
35.
The thujone-derived enone 1 , upon base-catalyzed reaction with 2-methyl-6-vinylpyridine is converted to the pyridine analogue 5 (Scheme 1). Catalytic reduction of the latter to 6 generates two new centers of chirality which eventually become C(8) and C(14) in the ultimate synthetic steroid analogue 12 . An X-ray analysis of 6 establishes the structure and absolute configuration so as to determine its suitability in subsequent synthetic studies. The acetal derivative 7 , via Birch reduction, hydrolysis, and internal aldol cyclization, is converted into the cyclohexenone analogue 10 (Scheme 2). This ‘one-pot’ process affords an efficient conversion of the pyridine ring into a cyclohexenone system required for A-ring construction of the steroid skeleton. Finally, conversion of 10 , via the unsaturated diketone 11 , provides the chiral steroid analogue 12 .  相似文献   
36.
Porous structure, acidity and hds activity of the CoMo–P–Al2O3 catalysts have been studied. Phosphorus was introduced jointly with molybdenum. This method of phosphorus incorporation gave substantial diminution of surface area, moderate changes of acidity and decrease in hds activity for the catalysts with P2O5 content higher than 5 wt.%.
, CoMo–P–Al2O3. . , P2O5 5 .%.
  相似文献   
37.
The F3CCl?FH and F3CCl?FCH3 dimers, which feature the halogen–halogen contacts, are investigated at MP2/6–311++G(d,p) and MP2/aug–cc–pVDZ levels of approximation. The binding energies of these complexes are found to be comparable to those of the weak hydrogen bonds. In both complexes the Cl?F are found to be significantly shorter than the sum of the corresponding van der Waals radii. The C–Cl?F contacts are also found to exhibit certain deviation from linearity. However, the energy differences between linear and bent structures are very small and primarily accounted for by electrostatic interactions between remote parts of the dimer. This indicates a high conformational flexibility of the halogen–halogen contacts and may help to explain the diversity of structural features in crystals formed by halogen-containing molecules. In both dimers the halogen–halogen interaction leads to certain shortening of the C–Cl electron accepting bond. This is accompanied by a small increase of the C–Cl stretching frequency. Hence, the two investigated dimers can possibly be classified as the blue-shifting halogen–halogen contacts.  相似文献   
38.
Four 9H and four 7H tautomers of DNA base xanthine were studied by the ab initio LCAO-MO method at the MP2/6-311G**//HF/6-31G** and MP2/6-31G**//HF/6-31G** approximations. All calculated structures are minima at the HF/6-31G** potential energy surface with the dioxo 7H tautomer (A1) being the global minimum. The second most stable tautomer, dioxo-9H (B1) is by 9 kcal/mol less stable. For the A1 B1 transition the calculated MP2 energy gap corresponds to the equilibrium constant of 2 × 10–7. Therefore, only the major tautomeric form A1 is predicted to be detectable in the gas phase. The 7H and 9H groups of tautomers are discussed separately. Within both groups, the dioxo form (A1-7H, B1-9H) is the most stable one and is succeeded by the 2-dihydroxy (A2, B2) form. However, while the energy difference between A1 and A2 is 10 kcal/mol, the energy difference between B1 a B2 is only 2 kcal/mol. The effect of polar environment was estimated by the SCRF method, using a spherical cavity, at the HF/6-31G** level. These calculations did not change the gas phase stability order of the tautomers. However, the energy difference between A1 and B1 decreased from 9 kcal/mol at the HF/6-31G** level to 4 kcal/mol at the SCRF HF/6-31G** level.  相似文献   
39.
On the Steric Course of the Reaction of Enamines Derived from Open-Chain Aldehydes and Ketones with Nitro-olefins Yielding 2,3-Disubstituted 4-Nitroketones The relative configuration of the nitro-ketone 12 obtained by the title reaction has been proved by a Baeyer-Villiger degradation and subsequent reduction to the amino-alcohol (±)-(u)- 20 , the relative configuration of which is identical with a sample prepared from 2-methyl-3-hydroxybutyrate of known configuration (Scheme 1). The stereochemical course of the title reaction is thus as predicted by our topological rule. It is assumed that the other nitro-ketones 13–18 described here are also formed by (lk)-combination of the trigonal centers of the educts (diastereoselectivity > 90%, see Formulae and Fig. 1). It is not possible to reverse this relative topicity by employing (Z)- instead of (E)-components of the starting materials, due to the reversibility of the primary step of these Michael additions (Schemes 2 and 3, and Fig. 2).  相似文献   
40.
The effects of intermolecular interactions on the second-order susceptibilities ((2)) of molecular crystals are studied by using a semiempirical quantum–chemical method. These effects are discussed on the basis of the super-molecular approach. The influence of the electrostatic interactions between adjacent unit cells on the tensor components of (2) was modeled by using the technique of cumulative atomic multipole moments (CAMMs).  相似文献   
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