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51.
The conformational flexibility of 1,4-dihydropyridine, 1,4-dihydropyrimidine, 1,4-dihydropyridazine, 1,4-dihydro-1,3,5-triazine, and their 4-oxo, imino, and methylene derivatives was studied by the semiempirical quantum-chemical AM1 method. It was demonstrated that the replacement of the methylene group in the dihydroazine ring by the exocyclic double bond results only in an increase in the rigidity of the heterocycle rather than leading to a loss of its conformational flexibility. It was suggested that nonplanar conformations of rings in ylide derivatives are stabilized by the nonaromatic cyclic -system. Introduction of the exocyclic double bond does not cause a substantial change in the -electronic structure of the heterocycle. The aromaticity indicesI
6 andI
6() were calculated. The correlation between these indices and a change in the energy upon bending of the heterocycle was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 8 pp 1938–1941, August, 1996. 相似文献
52.
钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用 总被引:3,自引:0,他引:3
用pH-电位滴定法测定了Pd(L)(Aa)+三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO3)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。 相似文献
53.
氯取代硫三碳菁染料的合成及性能 总被引:2,自引:1,他引:2
本文合成了七个硫三碳菁.其中四个具有桥环的菁染料。测定了它们的电子吸收光谱,讨论了结构对光稳定性的影响。并发现镍络合物能有效地抑制菁染料的光退色。 相似文献
54.
On the basis of the structures and properties of the ClO/ClO? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C1), 20.54 (EC2: C2, 2B), 20.69 (EC3: C1), 20.70 (EC4: Cs, 2A′), and 20.69 (EC.5: C2h, 2Bu) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
55.
A comparative quantum-chemical analysis of the electronic structures and spectroscopic parameters of the cycloalkanes C3H6, C4H8, C5H10, and C6H12 and their silicon analogs Si3H6, Si4H8, Si5H10 and Si6H12 was performed in the framework of the SCF MO LCAO method in the INDO approximation. Qualitative interpretation of “abnormal”
ionization potentials and energies of electronic absorption spectra of cyclopolysilanes has been given.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1105–1108, June, 1997. 相似文献
56.
A. V. Kazakova N. D. Kushch L. I. Buravov E. B. Yagubskii S. V. Simonov L. V. Zorina S. S. Khasanov R. P. Shibaeva E. Canadell J. Yamada M. Umemiya 《Russian Chemical Bulletin》2007,56(1):49-55
New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under
galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting
BDA-TTP layers alternate with the [Cu2Cl6]2− or [CuCl4]2− anions. Both salts show the semiconductor-type temperature dependence of the conductivity.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007. 相似文献
57.
58.
Colin Thomson 《Theoretical chemistry accounts》1973,32(2):93-100
Non-empirical LCAO-MO-SCF calculations on SiF2 using two Gaussian basis sets are reported. The larger basis set gives a calculated geometry in good agreement with experiment. The effect on the energy and population analysis of optimization of the Si 3d exponent was investigated. 3d orbitals are found to be much less important in the bonding than in the isoelectronic molecule SO2. 相似文献
59.
60.
The gas-phase electronic absorption spectra of (6-C6R6)2Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3dz2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO. 相似文献