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1.
The structure and conformational mobility of 4pentyl4cyanobiphenyl in the liquid and liquidcrystal states were investigated by means of IR spectroscopy (experiment and theory). IR absorption spectra in the frequency range 400–4000 cm-1 were measured in the temperature range 26–150°. Theoretical simulation of the IR spectra was performed using the fragment approach. A comparison of theoretical and experimental spectra showed that the examined samples were mixtures of conformers; characteristics of the most probable conformers are given. Temperaturerelated changes in the spectrum are due to the conformational mobility of the molecules, which is not high in the temperature range considered.  相似文献   

2.
The preferred conformation of solidphase R4benzylidene3,4dichloroaniline molecules has been established by nuclear quadrupole resonance (NQR) combined with quantum chemical calculations. The conformational effect of substitutes reported previously is proved. The rotation angle of the plane of the aniline ring with respect to the plane of the azomethine bond is given.  相似文献   

3.
An integrated Xray diffraction study was performed on polycrystals and single crystals of three new isostructural phases with general formula Ag4A2[M(NO2)4]3 (M = Pd, Pt; A = K, Rb). Data on the crystal structure solution (CAD4 diffractometer, MoK radiation, graphite monochromator = 2–30° are presented. In one crystallographically independent [M(NO2)4]2- complex anion, the planar square coordination of the central atom is completed to 4 + 2 by two oxygen atoms at a distance of 3.02–3.12 in the other anion, it is completed to 4 + 1 + 1 by an oxygen atom at a distance of 3.12–3.30 and an Ag+ cation at a distance of 3.04–3.11 . Part of the Ag+ cations form Ag - Ag dimers with a distance of 3.03–3.07. Crystalchemical analysis of known structures containing [Pd(NO2)4]2- complex anions was performed. It has been established that in none of the cases do any of the possible limiting configurations occur.  相似文献   

4.
The rates of cleavage of the Si–H bond of penta- and tetramethyldisiloxane have been studied. The reaction is first order in the silane and in the dilute acid. However, at high acid concentrations, the rate of reaction is governed by the acidity function of the system: this may indicate fast reversible proton transfer from the solvent to the organosilane in the rate-determining step.
Si–H - . . , : , .
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5.
An explanation is proposed for the nature of phase transitions in channel clathrates of thiourea with hexachloroethane and tetrachloroethane. Analysis of experimental temperature dependences of specific heat, entropy, and NQR spectra indicates the existence of first and secondorder phase transitions. In the thiourea + hexachloroethane compound, the secondorder phase transition (94.60 K, entropy gain Rln2) implies a transformation of two equiprobable states (lowtemperature phase) into a single new state (hightemperature phase). The firstorder phase transition corresponds to clathrate channel distortion. In the thiourea + tetrachloroethane compound, the secondorder phase transition (224K, entropy change Rln 6) occurs with transformation of six equiprobable states (lowtemperature phase) into a single new state (hightemperature phase). The firstorder phase transition corresponds to clathrate channel distortion. The next secondorder phase transition observed in this compound at 248 K leads to disappearance of the four possible orientations of guest molecules in the clathrate channel of hexagonal section and to a transition of guest molecules to chaotic orientation (entropy increment equals Rln 4).  相似文献   

6.
Xray structural investigation of the monoammonium salt of 5nitroaminotetrazole was performed. The crystals are orthorhombic: a = 10.077(1), b = 17.009(1), c = 6.6472(6), V = 1139.33(17)3, space group Pbca, Z =8, calc = 1.715 g/cm3. Monodeprotonation of 5nitroaminotetrazole during formation of the salt occurs at the N(4) nitrogen atom of the heterocycle. The anion has an almost flat structure; the bond lengths suggest delocalization of electron density in the molecule. The negative charge is distributed among three nitrogen atoms and two oxygen atoms of the anion. Changes in the geometrical parameters of 5nitroaminotetrazole on monodeprotonation are considered.  相似文献   

7.
The crystal and molecular structures of a guest–host complex of cucurbituril with 4methylpyridinium, {(4MePyH) (C36H36N24O12)}(NO3) · 4H2O, were determined by Xray structural analysis. The crystals are monoclinic with a = 26.276(3) , b = 25.861(2) , c = 17.375(2) , = 124.17(1)°, Vcell =9768.6(18) 3, space group Cc, and Z = 8. The structure contains two crystallographically independent supramolecular complexes. They are arranged in pillars oriented along the a axis. In each pillar, the complexes are parallel to each other. The pillars are shifted with respect to each other by onehalf of the crystallographic translation. The centers of the supermolecules are arranged according to a pseudobodycentered motif. Distortions of the cucurbituril molecule depending on the guest type have been analyzed with the use of results obtained in the present and previous studies.  相似文献   

8.
Tartaric acidmodified Raney nickel (TAMRNi) is an enantiodifferentiating catalyst for hydrogenation of ketones. The stereochemical models explaining the enantiodifferentiation of ketoester and 2alkanone were unified as an extended stereochemical model by the experimental supports. Based on this new model, a working hypothesis to improve the enantiomeric excess (ee) of the ketoester/TAMRNi system was developed, and the ee was improved to 96%. By further fine tuning of this system, almost perfect enantiodifferentiation resulting in over 98% ee was achieved.  相似文献   

9.
Developing the previously tested approach to the configurational and conformational analysis of cyclic chiral compounds based on a complex use of NMR spectra and molecular simulation, we determined the configuration 1R, 2R, 4R, 1S and conformational state of 2[1hydroxy1(4carbomethoxyphenyl) methyl]pmenthane3one, a minor product of the directed aldol reaction of (–)menthone with 4carbomethoxybenzaldehyde. The configurations of the cyclic chiral centers were determined by analysis of the spin–spin coupling constants of the protons of the cyclohexanone ring for the most probable conformations of alternative stereoisomers. The S configuration of the C (1) exocyclic chiral center was established from the different orientation of the benzene ring relative to the cyclohexanone fragment in alternative stereoisomers, as shown by semiempirical quantumchemical simulations (AM1 and PM3 methods), and from the observed difference in proton chemical shift between the examined hydroxyketone and the model (+)isomenthone (1R, 4Rdiastereomer).  相似文献   

10.
Kinetic parameters of thermal decomposition of compounds of general formulaM 2 I M II[Ni(NO2)6], whereM I= K+, Rb+ or Cs+ andM II= Ca2+, Sr2+ or Ba2+, were investigated on the basis of the respective thermal curves. Calculations of the reaction order and activation energy carried out by the Coats-Redfern method and by Doyle's method (modified by Zsakó) gave similar results, The reaction order is 2 for all the compounds investigated. In the group of potassium salts the activation energy increases fromM II=Ca2+ toM II=Ba2+. In the groups of rubidium and caesium salts, the lowest activation energy is observed whenM II=Sr2+. Such behaviour of the nitritonickelates is explained in terms of structures and the principle of maximum density.
Zusammenfassung Die kinetischen Parameter der thermischen Zersetzung von Verbindungen der allgemeinen FormelM 2 I M II [Ni(NO2)6] (M I= K+, Rb+ oder Cs+ und MII = =Ca2+, Sr2+ oder Ba2+) wurden auf Grund der entsprechenden thermischen Kurven untersucht. Die an Hand der Coats-Redfern Methode und der durch Zsakó modifizierten Doyleschen Methode durchgeführten Berechnungen der Reaktionsordnung und der Aktivierungsenergie ergaben ähnliche Resultate. Die Reaktionsordnung ist 2 für sämtliche untersuchten Verbindungen. In der Gruppe der Kaliumsalze steigt die Aktivierungsenergie vonM II=Ca2+ in RichtungM II=Ba2+ an. In der Gruppe der Rubidium- und Caesiumsalze wird die niedrigste Aktivierungsenergie beiM II=Sr2+ beobachtet. Dieses Verhalten der Nitritonickelate wird durch die Strukturen und das Prinzip der maximalen Dichte erklärt.

1 2 II[Ni(NO2)6], I= +, Rb+Cs+,a II= 2+,8r2+2+. , - ( ), . 2. + 2+. II=S2+. .
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11.
Single crystals of [Ni(Phen)(iBu2PS2)2] (I) and [Ni(Phen)3](iBu2PS2)2 (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F hkl , R = 0.0373 for I and 2575 F hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)3, Z = 4, calc = 1.255 g/cm3, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)3, Z = 4, calc = 1.292 g/cm3, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)3]2+ complex cations and i Bu2PS2 - outersphere anions. The NiN2S4 coordination polyhedra in the structure of I and NiN6 in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)2(iBu2PS2)](iBu2PS2) (II), and III is considered, as well as the packing modes of these complexes.  相似文献   

12.
A squareplanar [AuL2]+ gold(III) complex [L2 = 6.13dichloro5,7,12,14tetramethyl1,4,8,11tetraaza4,6,11,13tetraenato(2-)] containing two chlorine atoms in the position of the ligand hexacyclic ring was first synthesized by the reaction of the [AuL1]+ tetraiminate complex [L1 = 5,7,12,14tetramethyl1,4,8,11tetraaza4,6,11,13tetraenato(2-)] with HAuCl4 in an acetone – DMFA solution. The complex was isolated in the form of dichloroaurite (I), perchlorate (II), and tetrachloroaurate (III). Compounds I–III were studied by elemental and Xray diffraction analyses and IR and NMR spectroscopies. Single crystals of [AuL2]ClO4 were obtained, and the crystal structure of this compound was determined from Xray diffraction patterns. The crystals are monoclinic: a = 10.147(2), b = 7.260(1), c = 12.519(2), = 96.70(1)°, V = 915.9(3)3, Z = 2, space group P2/c, dcalc = 2.218, dmeas = 2.209 g/cm3 The crystal structure is built of nearly planar [Au(C14H20N4Cl2)]+ cations and [ClO4]- anions. Introduction of chlorine atoms into the positions of the hexacyclic rings of the tetraazamacrocycle hardly changes the lengths of the delocalized C N and C C bonds.  相似文献   

13.
The oxygen dependent cleavage of 9, 10-phenanthrenequinone by CuX (X=Cl, Br) with py, dipy, and phen ligands to well define copper(II) diphenato complexes and evidence for the intermediate Cu–O2 complexes containing CuII and CuI are reported.
9,10- CuX (X=Cl, Br) py, dipy phen (II), , , Cu–O2, CuII CuI.
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14.
15.
The structure of 2,3pentamethylene3,4dihydroquinazolone4 nitrate was determined by means of Xray diffraction. Analysis was performed of the geometry of the heterocyclic ring in 2,3tri, tetra, and pentamethylene3,4dihydroquinazolones4, quinazolines, and their salts with inorganic acids and complexes with metal ions. It is found that in the N(1)—C(2)—N(3) fragment in the bases of quinazolines and quinazolones4, the conjugation is less pronounced than that in the protonated (salt) forms.  相似文献   

16.
Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H2O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H2O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.  相似文献   

17.
HF and CAS calculations for linear geometry of Fe(CH)2 with symmetry have been performed. The basis sets used were DZ and DZ + P with ECP on the iron atom. Two closedshell and one quintet RHF wave functions have been found, and . All of them are singlet and triplet unstable in the wide range of Fe–CH distances. Singlet instability leads to the Charge Density Wave (CDW) brokensymmetry wave function with two electrons on carbon or orbital in the dissociation limit. Triplet instabilities lead to two brokensymmetry HF wave functions of Axial Spin Density Wave (ASDW) type, ASDW1 and ASDW2. In the dissociation limit they give carbon atoms with two electrons on and orbitals coupled to singlet and triplet, respectively. The stability conditions for CDW, ASDW1 and ASDW2 instabilities have been derived. Other HF wave functions with spin symmetry unrestricted have been also found. CAS(8,8), CAS(10,10) and CAS(12,12) calculations for singlet, triplet and quintet states of Fe(CH)2 have been carried out. In all CAS calculations the singlet state has the lowest energy. The Fe–CH equilibrium distances obtained from closedshell RHF wave functions are much shorter and from brokensymmetry wave functions are much longer than those obtained from CAS calculations.  相似文献   

18.
Complexes of the composition Pd(NOn)2–mClmL2 (n=2, 3; m=0, 1, 2; L=CH3CN) have been synthesized and their reactivity in ethylene and propylene oxidation has been examined. Data on the influence of the ligands, solvents and olefins on the composition of reaction products are reported.
Pd(NOn)2–mClmL2 (n=2, 3; m=0, 1, 2; L=CH3CN) . , .
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19.
Ab initio calculations of gasphase fluoroolefins with F or CF3 groups as substituents at the C=C double bond were performed using secondorder Möller–Plesset perturbation theory (MP2) with the 6–31G* and augccpVDZ basis sets and full geometry optimization. Geometrical parameters, singleelectron energies, electrondensity distributions, dipole moments, polarizabilities, and hyperpolarizabilities were computed. Variations in the electronic structure of fluoroolefins were analyzed and compared with variations in their physicochemical properties and reactivity.  相似文献   

20.
The paper describes synthesis of (nBu4N)2[RuNOCl5](I), (nBu4N)2[RuNOCl4OH](II), (nBu4N)2×[RuNOCl4OH]·6H2O (III), and (nBu4N)2[RuNOCl5]· 2(nBu4N)2[RuNOCl4(H2O)]·2H2O (IV). The complexes were studied by IR spectroscopy and powder Xray and crystal Xray analyses. The structures are built up of [RuNOCl5]2- (I, IV), [RuNOCl4OH]2- (II, III), and [RuNOCl4(H2O)]- (IV) complex anions, (nBu4N)+ cations, and crystal water molecules (III, IV). The substances are moderately soluble in water; highly soluble in polar organic solvents, such as acetone, ethanol, chloroform, methylene chloride; and almost insoluble in carbon tetrachloride and toluene. Under storage in light, the compounds decompose from the surface; in darkness I and II are stable, whereas III and IV can lose part of the crystal water.  相似文献   

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