共查询到20条相似文献,搜索用时 15 毫秒
1.
J. Hanuza M. M
czka A. Wa
kowska W. Oganowski H. Ban-Oganowska E. T. G. Lutz J. H. van der Maas 《Journal of Molecular Structure》1998,450(1-3)
The crystal structure of 2,6-dimethyl-4-nitropyridine N-oxide (DMNPO) has been determined at ambient temperature. The compound crystallizes as a monoclinic structure, space group P2/n, with 12 molecules per unit cell. The unit cell contains three non-equivalent formula units. The nitro group is not coplanar with the pyridine ring. Through a system of =C–HO hydrogen bonds the molecules are arranged into a two-dimensional network of layers parallel to the axc plane.The IR and Raman spectra, measured in the 3500–100 cm−1 region at ambient temperature, are correlated with X-ray structural data. The assignment of IR and Raman bands is given. The appearance of characteristic vibrational features in the spectra of this compound and the observed shifts of the =C–H and N–O IR active stretching modes, when the sample is dissolved in CCl4, is discussed in terms of the relatively strong =C–HO hydrogen bonds present in this crystal. 相似文献
2.
Robin D. Rogers Rodger F. Henry Leo A. Ochrymowycz Steven G. Toske 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(2):145-152
An improved synthesis of 20-thiocrown-4 is reported, which exploits the Kellogg method of cesium carbonate in DMF mediated macrocyclization of precondensed synthones which converge at the cycloicosane structure. The crystal structure of 20-thiocrown-4 reveals a rectangular conformation for the free ligand. Each sulfur is in onegauche and oneanti torsion angle. Four carbon positions make up the corners. There are two short sides comprised of –C–C– torsion angle sequencesg
–ag– and two long sides (aaa, g
–ag+). The S–C and C–C bond distances average 1.816(2) and 1.523(3) , respectively.
Supplementary data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82147 (9 pages) 相似文献
3.
The adsorption and isomerization of cyclopropane on the calcium- and sodium-exchanged zeolite Y are studied by IR spectroscopy. Cyclopropane is adsorbed on CaY in two different forms. Weaker adsorption is related to residual sodium ions, which were not completely removed from the zeolite by ion exchange. This form can be removed from the surface after evacuation of the samples at room temperature. Stronger adsorption is attributed to the Ca ions. It is stable up to 100°C. The corresponding diffuse-reflectance spectrum indicates the C
2v symmetry of the cyclopropane complex with Ca ions. At 200°C cyclopropane adsorbed on the calcium-exchanged zeolite converts to propylene. On the sodium-exchanged zeolite, this reaction only occurs at 400°C. The reaction coordinate of cyclopropane isomerization on CaY is related to the simultaneous cleavage of the C–C bond in the cyclopropane ring and hydrogen atom transfer from one of the CH2 fragments to another. The reaction coordinate corresponds to a combination of the stretching vibration of the C–C bond with the fan vibration of the CH2 group and the stretching vibration of the CH bond. These composite vibrations result in the strong polarization of the C–C and C–H bonds and, hence, exhibit anomalously high molar absorption coefficients in the IR spectrum. 相似文献
4.
The effect of solvent polarity versus specific C–HO contacts on the vibrational νC–H mode is studied using CHCl3 as a model system. Ab initio SCI–PCM calculations show that the overall shift of the νC–H band, sometimes ascribed to the C–HO hydrogen bonding, can in fact be explained by the electrostatic interaction with a dielectric environment. The presence of a new νC–H band – assigned to the C–HO bonded forms – remains as the most reliable evidence of C–HO hydrogen bonding. 相似文献
5.
The equilibrium structures, binding energies, and vibrational spectra of the clusters CH3F(HF)1 n 3 and CH2F2(HF)1 n 3 have been investigated with the aid of large-scale ab initio calculations performed at the Møller–Plesset second-order level. In all complexes, a strong C–FH–F halogen–hydrogen bond is formed. For the cases n = 2 and n = 3, blue-shifting C–HF–H hydrogen bonds are formed additionally. Blue shifts are, however, encountered for all C–H stretching vibrations of the fluoromethanes in all complexes, whether they take part in a hydrogen bond or not, in particular also for n = 1. For the case n = 3, blue shifts of the ν(C–H) stretching vibrational modes larger than 50 cm−1 are predicted. As with the previously treated case of CHF3(HF)1 n 3 complexes (A. Karpfen, E. S. Kryachko, J. Phys. Chem. A 107 (2003) 9724), the typical blue-shifting properties are to a large degree determined by the presence of a strong C–FH–F halogen–hydrogen bond. Therefore, the term blue-shifted appears more appropriate for this class of complexes. Stretching the C–F bond of a fluoromethane by forming a halogen–hydrogen bond causes a shortening of all C–H bonds. The shortening of the C–H bonds is proportional to the stretching of the C–F bond. 相似文献
6.
I. Juchnovski I. raschkov I. Panayotov 《Monatshefte für Chemie / Chemical Monthly》1970,101(6):1712-1719
Zusammenfassung Die IR-Spektren (670–2000 cm–1) der Metallketyle von Benzophenon, 1-Benzoylnaphthalin, 4-Benzoylbiphenyl, 3-Benzoylphenanthren, p-Tolylphenylketon, Triphenylacetophenon, Fluorenon, Xanthon und Benzanthron, die aus den Ausgangsketonen und Alkalimetallen in Tetrahydrofuran(THF) erhalten wurden, wurden gemessen. Die Umsetzung der Ketone in Ketyle führt zu starker Lockerung der C=O-Bindung sowie zu Frequenzerniedrigung der nichtebenen Deformations-schwingungen der C–H-Bindung, die von Größe und Bau des konjugierten Systems abhängen. Die IR-Spektren wurden zur Untersuchung der Oxydation von Ketylen und der Elektronen-übergänge zwischen Metallketylen und neutralen Molekülen der genannten Ketone herangezogen.
IR spectra of ketyls of some aromatic ketones and electron transitions between ketyls and neutral molecules
The IR spectra (670–2000 cm–1) of the metal ketyls of benzophenone, 1-benzoylnaphthalene, 4-benzoylbiphenyl, 3-benzoylphenanthrene, p-tolyl-phenylketone, triphenylacetophenone, fluorenone, xanthone and benzanthrone prepared from the corresponding ketones and alkali metals inTHF are investigated. The transformation of the ketones into ketyls leads to a considerable loosening of the C=O bond and to a decrease of the frequency of the C–H out-of-plane bending vibrations which depends on the size and structure of the conjugated system. The IR spectra are used for the study of the oxidation of ketyls and the electron transitions between the metal ketyls and the neutral molecules of the ketones investigated.相似文献
7.
William N. Setzer Gregory J. Grant Edward J. Meehan Sabrina D. Lee Rebecca M. Kirk Chin-Rang Yang Chia-Kuei Wu 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(4):649-656
Several metal complexes of the twenty-membered ring hexathioether macrocycle, 1,4,7,11,14,17-hexathiacycloeicosane (20S6), have now been prepared and crystallographically characterized. In order to examine structural changes in the ligand which may occur under complexation, we undertook an analysis of the structure of the 20S6 ligand by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group C2/c with the unit cell dimensions: a = 22.481(1) Å, b = 5.433(2) Å, c = 17.9259(9) Å, and = 117.711(4)°. The conformation adopted by this ligand is such that four of the sulfur atoms are exodentate, but two sulfur atoms are syn endodentate, unusual for a macrocycle of this type. All twelve of the C—S—C—C torsional bond angles in 20S6 are gauche as expected, and the ligand conformation may account for the complexation properties observed for this hexathioether macrocycle. 相似文献
8.
V. I. Evreinov S. V. Trepalin V. E. Baulin V. Kh. Syundyukova E. N. Tsvetkov 《Russian Chemical Bulletin》1992,41(4):687-691
The interaction of phosphorus-containing monopodands with Li+, Na+, and K+ cations in anhydrous CH3CN has been studied by FTIR spectroscopy. It has been shown that phosphoryl groups of the ligands take part in the formation of complexes with the alkali metal cation. The IR results obtained do not permit a clear conclusion as to whether or not the ether oxygen atoms of the ligand polyether chain participate in the complexation. It is suggested that in CH
3
CN the formation of 1:1 complexes is not accompanied by conformational reorganization of the monopodand.Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 884–889, April, 1992. 相似文献
9.
The mechanism of IR multiphoton dissociation of triethylsilane (TES) in the collision-free mode was studied. The principal unimolecular reactions are the C–Si and C–C bond rupture. The reactions of molecular elimination of CH4, C2H4, and C3H6do not play a substantial part in the mechanism of chemical transformations of TES. The spontaneous fragmentation of C2H5and (C2H5)2Si(CH2)H radicals produced by C–Si and C–C bond rupture, respectively, was shown to be feasible. 相似文献
10.
C–C bond rupture upon the oxidation of alcohols in the Fe(ClO4)3+ H2O2system in aqueous acetonitrile at room temperature is found. The relative yield of the products of C–C bond rupture is 20–30% under standard conditions for C2and C3alcohols and decreases in the series C2> C3> C4> C6. The alkyl radical and carboxylic acid are the products of C–C bond rupture in alcohol oxidation. Cyclohexane is a competitive inhibiting agent for C–H bond oxidation in 1-propanol, and it does not affect the yield of the products of C–C bond rupture. When H2O2is replaced by tert-BuOOH, the fraction of the products of C–C bond rupture decreases by an order of magnitude. Our data suggest that a non-radical intermediate, likely Fe(III) hydroperoxo complex, is responsible for C–C bond rupture in alcohol under the reaction conditions. 相似文献
11.
Chuan-Jiang Qiu Yue-Cheng Zhang Yu Gao Ji-Quan Zhao 《Journal of organometallic chemistry》2009,694(21):3418-3424
Methyltrioxorhenium (MTO) forms complexes with Schiff-bases derived from 2-pyridinecarboxaldehyde and amines. These complexes were isolated and fully characterized by NMR, IR, UV–Vis, EA, MS. Two were analyzed by X-ray crystallography, which showed that the compounds display distorted octahedral geometry in the solid state with a trans-position of Schiff-base ligand. The characterized results indicated that the more Lewis basic the ligand is, the stronger the metal–ligand interaction between the rhenium atom and the ligand. The complexes displayed high catalytic activity and selectivity when applied to the epoxidation of cyclohexene with urea hydrogen peroxide adduct (UHP) as oxidant in methanol, but poor performances with hydrogen peroxide (30%) as oxidant due to their decomposition. Experimental results revealed that the MTO Schiff-base complexes are, in general, more sensitive to water than MTO itself. Moreover, large excess of ligand is detrimental to the catalytic performance as it leads to the decomposition of the complexes. 相似文献
12.
The properties of alkylbenzenes were estimated, using the contributions of the σ bonds, the conjugated π bond and the steric effect in alkylbenzene molecule. And a novel bond orbital-connection matrix, conjugated π bond orbital-connection matrix in aromatic molecules, was proposed. The eigenvalues of the conjugated π bond orbital-connection matrix can well express the contribution of the conjugated π bond to the properties of aromatic molecules. Using this eigenvalue together with the parameters proposed in our early works, the bond orbital-connection matrix method was extended successfully to the QSPR studies of alkylbenzenes and a general model was obtained to evaluate the thermochemical properties of alkylbenzenes, that is,
p(alkylbenzene)=aNC–C+b∑X1CC+cNC–H+d∑X1CH+eSZ/E+k∑X1π,