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1.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
2.
Hidetaka Tobita 《Journal of Polymer Science.Polymer Physics》2004,42(14):2801-2812
The matrix formula developed in the context of heterochain theory, M?w = M?wp + WF ( I ? M )?1 S , was applied to describe the molecular weight development during free‐radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic‐rate constants and the various concentrations associated with them. In free‐radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight‐average molecular weights. The moment equations with the average pseudo‐kinetic‐rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2801–2812, 2004 相似文献
3.
《Magnetic resonance in chemistry : MRC》2003,41(8):626-628
15N isotopic enrichment was necessary for the unequivocal assignment of the 1H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C6H5CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, 1J(15N,1H) = 102.2 Hz, 2J(15N,1H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the 29Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
4.
R. Murugesan P. Sami T. Jeyabalan A. Shunmugasundaram 《Journal of Chemical Sciences》1995,107(1):1-10
Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with
bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [TiIIITiIVW10PO40]8− is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron
is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to
be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K5MII[Ti2W10PO40].xH2O(MII = Cu or Mn) are isomorphous with K7[Ti2W10PO40].6H2O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K5MII[Ti2W10PO40].xH2O complexes. This high symmetry is confirmed in K5Cu[Ti2W10PO40] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K. 相似文献
5.
Stationary phase properties of the organic molten salt ethylpyridinium bromide in gas chromatography
Summary The organic molten salt, 1-ethylpyridinium bromide, is suitable for use as a stationary phase in gas chromatography. It has a usable liquid temperature range of 110 to 160°C. It undergoes a single phase transition at 110°C which corresponds to the bulk melting point. Below the melting point the phase may be used as a selective adsorbent, although column efficiency and peak symmetry deteriorate as the temperature is lowered from the melting point. Above the melting point, ethylpyridinium bromide can be used to separate a wide variety of organic compounds retaining strongly those compounds possessing large dipole or hydrogen bonding functional groups. 相似文献
6.
J. Goubeau 《Angewandte Chemie (International ed. in English)》1966,5(6):567-578
The force constants and the corresponding bond orders of nitrogen bonds have been calculated from the vibrational spectra (infrared and Raman spectra) of a great number of nitrogen compounds. Plotting the maximum bond order of stable nitrogen bonds against the sum of Pauling's electronegativities of the bonding partners (Σx) leads to one continuous curve for the N? X bonds where X represents elements of the first and the second short period of the periodic table. Furthermore, when the bonds formed between these elements are arranged in a coordinate system in such a way that the position of each bond is determined by the difference between the electronegativities of the bonding partners (Δx along the ordinate) and the sum of the electronegativities of the bonding partners (Σx along the abscissa), the bonding partners capable of forming multiple bonds all lie within a closed domain, where their position can be correlated with their polymerizability and other reactivities of the multiple bonds. Also discussed are the orders of bonds between nitrogen and some transition elements. In an appendix, the present methods used to calculate force constants and bond orders are surveyed. 相似文献
7.
Jasmina M. Dimitrić Marković Zoran S. Marković Jelisaveta M. Baranac Marina L. Dašić 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1225-1232
Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations.
In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted
the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical
calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by
chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it
is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power. 相似文献
8.
The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H2NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm–3 in NaClO4 as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP)
2
2–
, Zn(NMP) and Zn(NMP)
2
2–
, refined by the MINIGLASS program, are reported. 相似文献
9.
T. P. Elango V. Ramakrishnan S. Vancheesan J. C. Kuriacose 《Journal of Chemical Sciences》1984,93(1):47-52
Rate constants for the reaction of carbonate radical with aniline and some parasubstituted anilines have been determined by
the flash photolysis technique. Using σ+ para values the rate constants at pH 8.5 correlate very well with the Hammett equation yielding ρ= − 1. The carbonate radical oxidises aniline giving the anilino radical. The products so formed have been identified through
studies under conditions of continuous irradiation. 相似文献
10.
This paper reports our results for the direct experimental determination of the equilibrium constant for the hydrogen-isotope-exchange
reaction, 1/2D2(g)+HCl(hexOH)=1/2H2(g)+DCl(hexOD), where hexOH isn-hexanol and hexOD isn-hexanol with deuterium substitution in the alcohol function. The reaction was studied in electrochemical double cells without
liquid junction for which the net cell reaction is the above isotope-exchange reaction. The experimentally determined value
of ε° (296.0°K) for this cell is 4.03±0.95 mV (strong electrolyte standard states, mole-fraction composition scale); the value
of the equilibrium constant for the reaction is 1.17±0.05. The contributions of isotope-exchange and transfer effects to the
magnitude of the standard Gibbs energy change for the above reaction and for the analogous reaction 1/2D2(g)+HCl(aq)=DCl(daq)+1/2H2(g) are considered. Our results support the conclusion of Heinzinger and Weston that the formulation of the solvated proton
in water as H3O+, as opposed to H9O4
+, is sufficient for the interpretation of the thermodynamics of hydrogen-isotope-exchange reactions in water. We also find
that the formulation of the solvated proton inn-hexanol as ROH
2
+
is sufficient for the interpretation of our results on the thermodynamics of hydrogen-isotope-exchange inn-hexanol. 相似文献