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991.
A new molybdenum(V) diphosphate KMoP2O8 has been isolated. The single crystal X-ray diffraction study of this phase has shown that it is isotypic with KNbP2O8. It crystallizes in the P21/n space group a = 5.0862(4), b = 11.720(1), c = 11.486(1) Å, β = 90.91(1)°. The structure of this phase is compared with those of other molybdenum(V) diphosphates. This tunnel structure is described in terms of [MP2O8]8∞ ribbons running along ā, showing close relationships with the titanophosphate NaTiP2O7. The existence of one free apex for each MoO6 octahedron and each P2O7 group, respectively, is emphasized, allowing a great flexibility of the structure. 相似文献
992.
P. I. Dem'yanov E. M. Myshakin D. P. Krut'ko V. S. Petrosyan 《Russian Chemical Bulletin》1997,46(12):1996-2005
The results of calculations for benzyl chlorides and benzyl bromides that contain substituents in the ring by different quantum-chemical
methods are compared. The electron density on the benzyl carbon atom increases as the electron-withdrawing properties of substituents
are enhanced due to the shift of the electron density from the benzyl halogen atom to the adjacent carbon atom. A topological
analysis according to Bader confirmed the main reason for the change in the paramagnetic shielding of the benzyl13C nuclei. The results of calculations provide, for the first time, an explanation for the resonance upfield13C shift of this atom as the Hammett constant of a substituent increases in compounds of the series under consideration.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2111–2119, December, 1997. 相似文献
993.
已报导,经适当处理的SO42-ZrO2和WO3-ZrO2具有超强酸性[1].在此基础上将SO42-和WO3同时负载于ZrO2表面,发现其表面酸性有明显增强,得到的固体超强酸504-W0s-Zro。在很宽的焙烧温度范围内(700七00“C)都具有HO三一16.04的酸强度,吸附毗院的红外光谱研究表明,其表面同时具有强的L酸性和B酸性问,140“C时,对正乙烷裂解及异构化的催化活性比SO4--ZrO。和WO3-ZI02都高,表现出相当的协同效应同.本文用XRD,DTA-TG,比表面测定等技术研究催化剂的组成、结构形态及其随焙烧温度的变化.并与504-Zro:和WO。… 相似文献
994.
995.
Cage organometallosiloxanes were synthesized according to a new procedure using monomeric organoalkoxysilanes as the starting
compounds. The latter were subjected to hydrolysis immediately before the exchange reaction of sodium silanolate with metal
halides. Difficultly accessible metallovinylsiloxanes, metallomethylsiloxanes, and metallosiloxanes containing a functional
group in the organic radical at the silicon atom can be readily prepared according to the method proposed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2530–2532, December, 1998. 相似文献
996.
Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)2+3] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and
-gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)3+3below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)2+3*. The factors which affect the determination and HPLC separation of the four acids were also investigated. 相似文献
997.
Anna Chrostowska Véronique Métail Geneviève Pfister-Guillouzo Jean-Claude Guillemin 《Journal of organometallic chemistry》1998,570(2):5188
Primary vinylic and acetylenic germanes and stannanes, synthesized by a chemoselective reduction of the corresponding trichloro derivatives, were investigated by ab initio quantum chemical methods and photoelectron spectroscopy. In particular, the PE spectra display very well-resolved bands which show the increasing destabilizing effect of 14 group heteroatom α-substitution of double or triple carbon–carbon bonds. 相似文献
998.
GuoHongLI YueMaoSHEN KeQinZHANG 《中国化学快报》2005,16(3):359-361
A novel saponin was isolated from the transformed products of ginsenoside Rh1 by Bacillus subtilis. It‘s structure was determined to be 3-O-β-D-glucopyranosyl-6-O-β-D-glucopyranosyl-20 (S)-protopanaxatriol on the basis of the spectral data. 相似文献
999.
Density functional (BLYP, B3LYP and BHLYP) and highly correlated MP2 and CCSD(T) calculations have been performed to investigate conformers, energy barriers, intramolecular H-bond strength, gas-phase basicity and deprotonation energies of glyoxilic acid oxime (gao) and related ions in gas phase and in aqueous solution (SCRF-PCM method). BHLYP/6-311G(d,p) and B3LYP/6-31++G(d) predictions for the global minimum conformer of gao were consistent with experiment. BLYP level overestimated the H-bond and stabilized incorrectly the H-bonded conformer. The calculations in solution indicated destabilization of H-bonded conformers due to the small polarizability and weaken of the H-bond. The same global minimum structures in gas phase and aqueous solution were found for gao-neutral (ectt) and gao-dianion (e−2), whereas they were different for gao-anion because of the strong decrease of the conformational energies in solution. The global minimum structures of the neutral, anion and dianion of gao, obtained in solution, are in agreement with experiment. The gas-phase basicity (GB) and molecular electrostatic potential (MEP) calculations revealed the same sites for electrophilic attack, supported by the nature of HOMO: the carbonylic oxygen for the neutral, the carboxylic oxygen for the anion and the oxime nitrogen for the dianion. MEP results in gas phase and in solution suggested a region between the two atoms, but not on one atom in accordance with bidentate binding of gao ions to a metal. The BHLYP/6-31++G(d,p) molecular properties of gao were in best consistent with CCSD(T) results. The thermodynamical properties (GB and bond deprotonation energy) of gao were better estimated at B3LYP level. 相似文献
1000.
Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD3OD/(D6)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents. 相似文献