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21.
Venkataraman Vishwanathan Gajula Balakrishna Balraj Rajesh Venkatreddy Jayasri Lucky Sikhwivhilu Neil J. Coville 《Reaction Kinetics and Catalysis Letters》2007,92(2):311-317
A series of sulphate-promoted ZrO2 solid acid catalysts with different contents of SO4
2− were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow
reactor. The 5 wt.% SO4
2− on ZrO2 showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was
observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism
is proposed. 相似文献
22.
We define the Lie algebrac(n) of centrosymmetric matrices. It generates a noncompact and nonsemisimple local Lie group with the unusual property that expc(n) c(n). The group contains an invariant subgroup of Lorentz boost/ dilation transformations. Forn even, these form a subgroup of the conformal group of the Lorentzian metric with signature (– + – + – +). 相似文献
23.
The behavior of the equioscillation points (alternants) for the error in best uniform approximation on [–1, 1] by rational functions of degreen is investigated. In general, the points of the alternants need not be dense in [–1, 1], even when approximation by rational functions of degree (m, n) is considered and asymptoticallym/n 1. We show, however, that if more thanO(logn) poles of the approximants stay at a positive distance from [–1, 1], then asymptotic denseness holds, at least for a subsequence. Furthermore, we obtain stronger distribution results when n (0 < 1) poles stay away from [–1, 1]. In the special case when a Markoff function is approximated, the distribution of the equioscillation points is related to the asymptotics for the degree of approximation.The research of this author was supported, in part, by NSF grant DMS 920-3659. 相似文献
24.
Ntaoleng M. Makunya Reinout Meijboom Alfred Muller 《Journal of organometallic chemistry》2005,690(18):4159-4167
Cyclopentadienyldicarbonylmethyliron, [CpFe(CO)2Me] (1), undergoes migratory carbonyl insertion under the influence of isosteric phosphine ligands P(4-FC6H4)3 and P(4-MeC6H4)3. The products of the reaction, [CpFe(CO)(COMe)P(4-FC6H4)3] (2a) and [CpFe(CO)(COMe)P(4-MeC6H4)3] (2b), were characterised by X-ray crystallography. In both structures, the iron atom adopts a pseudo octahedral coordination geometry. Fe-P bond distances are the same at 2.1932(8) Å in 2a and 2b, respectively. Thus, contrary to what was expected, X-ray data could not be used to quantitatively differentiate between the two phosphine ligands in 2a and 2b. Therefore, additional spectroscopic techniques such as IR and NMR were employed. Similarly, the Fe-C bond lengths of the carbonyl (Fe-CO) and acetyl (Fe-COMe) are 1.748(3) and 1.955(3) in 2a, and 1.744(3) and 1.951(3) Å in 2b, respectively.The migratory carbonyl insertion was studied by NMR, IR, and UV-vis spectroscopies to determine the mechanism and the rate law. Results from NMR spectroscopy show that the formation of the product is accompanied by oxidation of the corresponding phosphine ligand. An increase in the reactivity of migratory carbonyl insertion for P(4-MeC6H4)3 was observed when the solvent was changed from CH2Cl2 to MeCN. The kinetic data showed that P(4-MeC6H4)3 reacts faster than P(4-FC6H4)3. 相似文献
25.
RuCl2(PPH3)3 has been attached to a phosphinated polymer support (phosphinated polystyrene crosslinked with 2% divinylbenzene) and the reagent converted to the polymer supported analogue of RuClH(PPH3)3 in the presence of base. The polymer supported catalyst efficiently hydrogenates terminal olefins under ambient conditions. Hydrogenation of 1-hexene has revealed that the reaction rate is proportional to [Ru], [H2] and [olefin]/(1 + [olefin]). The polymer support environment allows for selectivity in olefin hydrogenation and under suitable reaction conditions short chain terminal olefins are hydrogenated more rapidly than long chain terminal olefins. The extent of metal loading on the polymer and the reaction solvent composition also influence the reaction selectivity and these effects are discussed. 相似文献
26.
The reaction of an aromatic lithium reagent, LiR, with a perfluoroacid anhydride (RfCO)2O, in ether solution at low temperatures, produces esters of composition in addition to the expected ketone . Mixed esters of composition may be prepared by starting with a ketone and reacting with a lithium reagent LiR followed by perfluoroacid anhyride (RfCO2O. Hydrolysis of the esters provide a convenient route to trertiary alcohols of composition Rf(R) 2COH. 相似文献
27.
Mokoena Emma M. Datye Abhaya K. Coville Neil J. 《Journal of Sol-Gel Science and Technology》2003,28(3):307-317
DL-tartaric acid was used as a template for the formation of silica nanotubes and spheres by the sol-gel method from tetraethylorthosilicate (TEOS) as silica source. The reactions were carried out in ethanol/water mixtures in the presence of aqueous ammonia, between 0°C and 75°C, using both stirred and non-stirred conditions. TEM and SEM images show that the yield and microstructure of the silica is influenced by the synthetic conditions (temperature, ammonia (aq) concentration, gelation time, solvent mixture). It was observed that the chiral form of the tartaric acid used and the diffusion of TEOS to the template determines the eventual silica structure. 相似文献
28.
H. Huber Ch. Koeberl I. McDonald W.U. Reimold 《Journal of Radioanalytical and Nuclear Chemistry》2000,244(3):603-607
We used - coincidence spectrometry to investigate the possible presence of a meteoritical component in 27 samples of South African diamictites. Recently, several studies have suggested that some tillites/diamictites may represent impact breccias, but a petrographical study by our group found no evidence for the presence of impact-characteristic shocked minerals. The siderophile elements, such as Cr, Co, Ni, and, especially, the platinum group elements, have high abundances in meteorites, but low abundances in terrestrial crustal rocks. The Ir content of the diamictites was measured with the new iridium coincidence spectrometer (ICS) at the University of Vienna, with detection limits of around 0.02 ppb. No enrichments in the contents of Ir and other siderophile elements compared to average crustal concentrations were found; thus, no unequivocal evidence for an impact origin of these diamictites of the South African Dwyka Group can be documented. 相似文献
29.
The infrared spectra in the OH-stretching and HOH-bending regions of H2O, and in the OH-stretching region of HDO dissolved in a number of ketones and ethers have been recorded. The number of component bands and their wavenumbers, halfwidths and intensities, as well as the total OH-stretching intensity in each solvent, have been interpreted in terms of a model for the types of hydrogen bonded solvent:water complexes formed in these systems.The effect of temperature on the spectra of H2O in some of the ketones has been rationalized on the basis of the equilibrium existing between the different hydrogen bonded species present in solution. 相似文献
30.
The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported. 相似文献