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21.
用~1HNMR方法研究了溶液中大环化合物1,12-二氮杂-3,4:9,10-二本并-5,8-二氧杂环十五烷-N,N’-二乙酸盐的构象.NMR变温实验表明,在溶液中大环与Zn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)的配合物环上醚氧不参与配位,其中Ni(Ⅱ)配合物为低自旋反磁性的平面四方形配位. 相似文献
22.
Yoshihiko Saito 《中国化学会会志》1991,38(5):405-424
A historical overview will be given on the structural studies on transition metal compounds and their interaction with other fields of coordination chemistry. About three decades have passed away since the structure and absolute configuration of tris(ethylenediamine)cobalt(III) complex ion were determined. At present accumulation of the structural data for isomers has enabled us to understand structural principles of chelate complexes in considerable detail. The energy minimization calculations can predict the detailed geometries of the complexes. Differences in thermodynamic properties between different conformers are well reproduced. Aspherical distribution of 3d electrons in transition metal complexes was detected for the first time in crystals of [Co(NH3)6][Co(CN)6] in 1973. Such an accurate electron density study provides important information on the d electrons placed in a ligand field. The high-spin and low-spin states can be distinguished unequivocally. In spite of a very small valence/total electron ratio, the asphericity of 4d and 5d electrons in a ligand field can be detected. The crystal structures of a series of dimeric copper(II) carboxylate adducts of the general formula [Cu(RCOO)2L]2 have been determined or redetermined as accurately as possible. The temperature dependent magnetic susceptibility of these crystals indicated that the isolated pairs of Cu(II) ions interact strongly through exchange forces. Molecular orbital calculations revealed that the electron population in the carbon atom of the bridging OCO group plays an important role in determining the strength of the spin superexchange interaction. In the crystals of some cobaloxime complexes, racemization of chiral groups bonded to Co proceeds on X-ray exposure without degradation of crystallinity. Several intermediate stages could be determined by X-ray analysis. Various reaction pathways were recognized and the reaction rate could be correlated with the atomic arrangement in the crystal. 相似文献
23.
24.
Magorzata A. Broda Maria Rospenk Dawid Siodak Barbara Rzeszotarska 《Journal of Molecular Structure》2005,740(1-3):17-24
The comparative studies on the association of Ac-ΔAla-NMe2 and Ac-l-Ala-NMe2 in carbon tetrachloride were performed by the analysis of their average molecular weight, dipole moments and FTIR spectra. To aid spectroscopic interpretation and gain some deeper insight into the nature of associates, the geometries of the minimum energy of the dimers of Ac-ΔAla-NMe2 and Ac-l-Ala-NMe2 were calculated by the B3LYP/6-31+G** method. The average molecular weight in the studied concentration range, for the ΔAla and l-Ala peptide, as determined by the osmometric method, did not exceed 1.5 and 1.2 of the monomeric mass, respectively. Accordingly, the percentage of the monomeric form (α) decreased as concentration was increased more significantly for the ΔAla analogue than for its saturated counterpart. In the studied concentrations, the dipole moment of the unsaturated compound decreases and that of its counterpart is almost constant. We identified a wider range of dimeric forms of Ac-ΔAla-NMe2 than those of Ac-l-Ala-NMe2. While Ac-ΔAla-NMe2 mainly forms cyclic dimers, built of open conformers H/F, specific for α,β-dehydroamino acids, Ac-l-Ala-NMe2 forms cyclic and linear dimers, characteristic for the usual amino acids. Ac-ΔAla-NMe2 has a greater tendency to associate than its saturated variant, which is the result of stronger hydrogen bonds. 相似文献
25.
使用疏水作用色谱研究蛋白质的构象变化 总被引:2,自引:0,他引:2
研究了高效疏水作用液相色谱中(HIC)色谱条件改变对蛋白质构象的影响。发现固定相配体的疏水性、温度及流动相中盐的阴离子、阳离子和pH值都影响蛋白质的构象。 相似文献
26.
在CCSD(T)/6-311G(d,f)//MP2/6-311G(d,f) ZPE水平下,计算得到含有8个异构体和11个过渡态的HSCCS自由基体系势能面,讨论了异构体的结构与稳定性及异构体之间的异构化过程.结果表明异构体m1的能量最低,除m1以外,异构体m2和m3的能量也比较低,在MP2水平上,过渡态TS1的能量比异构体m2仅高3.9kJ/mol,而在CCSD(T)水平上,TS1的能量比m2低14.6 kJ/mol,这说明异构体m2可以迅速转化为能量更低的m1.异构体m3的能量比异构体m1高49.99 kJ/mol,可以推断,在合适的实验条件下可以观测到异构体m1. 相似文献
27.
T. Kimura Y. Takahashi T. Kamiyama M. Fujisawa 《Journal of Thermal Analysis and Calorimetry》2007,88(2):587-595
Excess enthalpies (H
E)
of 17 binary mixtures of o- and m-isomers of dichlorobenzene, difluorobenzene, methoxymethylbenzene,
dimethylbenzene, dimethoxybenzene, aminofluorobenzene, fluoronitrobenzene,
diethylbenzene, chlorofluorobenzene, fluoroiodobenzene, bromofluorobenzene,
chloromethylbenzene, fluoromethylbenzene, bromomethylbenzene, iodomethylbenzene,
fluoromethoxybenzene, dibromobenzene at 298.15 K were measured. All excess
enthalpies measured were very small, and those of o-+m-isomers of aminofluorobenzene, dibromobenzene and
iodomethylbenzene were negative but 14 other binary mixtures of isomers were
positive over the whole range of mole fractions. H
E
of o-+m-isomers
of dimethoxybenzene showed the largest enthalpic instability and those of
aminofluorobenzene showed the largest enthalpic stability. There was a correlation
between dipole–dipole interaction, dipole–induced dipole interaction
or entropies of vaporization and excess partial molar enthalpies at infinite
dilution. 相似文献
28.
29.
DFT calculations have been performed to determine the isomer shift for a series of iron(II) clusters with nitrogen-containing ligands which serve as models of coordination units in Fe(II) complexes with 1,2,4-triazoles possessing a 1 A 1 ? 5 T 2 spin transition. Good agreement has been found between the theoretical and experimental values of the isomer shift for both low-and high-spin phases. Our calculations confirmed the hypothesis about relationship between the experimentally observed differences in the isomer shift for the low-spin phases of the complexes and variations of the Fe-N mean bond length. 相似文献
30.
Kenji Tonan Shun-ichi Ikawa 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2695-2700
Effect of pressure on conformational equilibria of a small peptide N-acetyl-l-Pro-l-Leu-Gly-NH2 in a chloroform solution has been studied by FTIR spectroscopy. Absorption in the NH stretching region was measured at pressures in the 1–1080 bar range and at 296 K, and decomposed into component bands by least-squares fitting. Intensity ratios of bands which were assigned to a hydrogen-bond-free conformer and intramolecularly hydrogen-bonded conformers with 10- and 13-membered hydrogen bonded rings, respectively, were examined as a function of pressure. It was found that the conformer with the 13-membered ring has definitely smaller partial molar volume than the other two conformers which have nearly the same volume with each other. On the basis of a simple dielectric model, we have shown that the conformer with the 13-membered hydrogen-bonded ring has a considerably large dipole moment which is consistent with the α-helical structure suggested by the previous variable-temperature FTIR study. 相似文献