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81.
Merlin Rosales Janeth Navarro Ligbel Sánchez Angel González Ysaías Alvarado Raúl Rubio Carlos De La Cruz Tamara Rajmankina 《Transition Metal Chemistry》1996,21(1):11-15
Summary The complex [RuH(CO)(NCMe)2(PPh3)2]BF4 (1) is an efficient and regioselective catalyst precursor for the hydrogenation of polyaromatic nitrogen compounds such as quinoline (Q), isoquinoline (iQ), indole (ln), 5,6- and 7,8-benzoquinoline (BQ) and acridine (A) under relatively mild reaction conditions (125 °C, 4 atm H2). The order of individual initial rates was: A > Q > 5,6-BQ > 7,8-BQ > ln > iQ, reflecting both steric and electronic effects. For the regioselective homogeneous hydrogenation of A to 9,10-dihydroacridine (DHA) catalysed by complex (1), a kinetic study was carried out; the experimentally determined rate law was r = k
1 [Ru] [H2]. These findings are consistent with a mechanism involving the hydrogenation of [RuH(CO)(A)(NCMe)(PPh3)2]BF4 to yield DHA and the unsaturated species [RuH(CO)(NCMe)(PPh3)2]BF4 in the rate-determining step. 相似文献
82.
Summary Magnetic susceptibilities of the biacetyldihydrazone (BdH) complexes [M(BdH)3](NO3)2 (M = CoII, NiII, CuII or ZnII), [Fe(BdH)3](NO3)3, [M(BdH)3](Ni(dto)2] (M = CoII, NiII or ZnII; dto = dithiooxalate), [(BdH)2Cu(dto)Ni(dto)] and [Fe(BdH)3]2[Ni(dto)2]3 have been studied in the 4.2–295 K range. ZnII complexes are diamagnetic, and complexes of NiII, CuII and FeIII obey the Curie-Weiss law. The CoII complexes behave anomalously and the results are interpreted in terms of a high spinlow spin equilibrium. 相似文献
83.
Marchante-Gayón JM González JM Fernández ML Blanco E Sanz-Medel A 《Analytical and bioanalytical chemistry》1996,355(5-6):615-622
A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes. 相似文献
84.
The two new diterpenes, vierol (1) [(?)kaurane-16α,18-diol] and powerol (3) [(?)kaurane-7β,16α-diol] have been isolated from Sideritis canariensis Ait. 1 was obtained by partial synthesis from epicandicandiol (7), and 3 was related with (?)kauranol (6) and (?)kauren-7β-ol acetate (11). Reduction of the acetoxy-aldehyde 14 by the method of Huang-Minlon and posterior acetylation gave 11, (?)isokauren-7β-ol acetate (17) and (?)kauran-7β-ol acetate (18). 相似文献
85.
V. Manríquez C. Díaz G. González I. Brito 《Journal of Thermal Analysis and Calorimetry》1996,46(6):1875-1880
Benzenesulfenamides with the formula R-S-N-(R)2 (R=C6H5 andR=NC4H8O, C7H7 and C6H11) and their chromium carbonyl complexes were studied by means of TG and mass spectrometric methods. The thermal behaviour of the compounds the stabilities of free sulfenamides are lower than those observed for the corresponding chromium carbonyl complexes. Combined thermogravimetry — mass spectrometry results suggest that the fragmentation mechanism of the carbonyl complexes involves cleavage of the Cr-S and Cr-CO bonds while that of sulfenamide depends mainly on the dissociation rates of the NR2 groups.This work was partially supported by the Departamento técnico de Investigation of the Universidad de Chile, Grant Q3280/9324. 相似文献
86.
Gracia CA Gómez-Barreiro S González-Pérez A Nimo J Rodríguez JR 《Journal of colloid and interface science》2004,276(2):408-413
Static (SLS) and dynamic (DLS) light-scattering techniques were applied to the study of the aggregation of dodecyl- (C12DBACl), tetradecyl- (C14DBACl), and hexadecyldimethylbenzylammonium (C16DBACl) chlorides in water and in 0.01 and 0.05 m NaCl aqueous solutions at 25 degrees C. Results of SLS measurements yielded critical micelle concentration (cmc) values for aqueous and NaCl solutions. The aggregation numbers of the micelles for the homologous surfactants are low but increase with chain length and ionic strength of the solution. Various patterns of changes of the diffusion coefficient, D, as a function of chain length, molality, and with ionic strength were found for the studied surfactants. Transformations in the structure of micelles of C14DBACl in 0.01 m NaCl occur at a concentration of surfactant of about 0.01 m. Such transformations, presumably due to rodlike structure, are the more extensive the higher the concentration of NaCl. The concentration of C16DBACl in 0.05 m NaCl covers the range where already repulsive interactions between micelles occur, as judged by the strongly negative slope of the D versus molality plot. To provide additional information on the suggested transformations, complementary viscosity measurements for C14DBACl in 0.01 m of NaCl have been performed. 相似文献
87.
González FR 《Journal of chromatography. A》2000,873(2):209-219
Non-linear regressions were applied to n-alkanes retention data for the determination of gas hold-up in a preceding paper. It was found that at temperatures over 100 degrees C the reduced partial molar free energy of solution, deltaG/RT, tends to be negligible for the solute methane in poly(dimethylsiloxane) stationary phases. A consequence of interest can be inferred from this fact. The C-H bonds from terminal methyl groups of n-alkane solute molecules should not contribute significantly to deltaG/RT in these conditions. The analysis of data confirms that, within the chromatographic experimental error, the contributions of n-alkane end C-H bonds are also negligible in this temperature range. Consequently, the regression parameter that contains the phase ratio of the column only includes the gas hold-up as the accompanying factor. 相似文献
88.
Experimental results on the electrophoretic velocity and mobility of Ca-montmorillonite in 2-propanol are reported. The variation of the electrophoretic velocity with the externally applied electric field and the particle size range, at constant volume fraction and temperature, is considered. Given the difficulties for determining the types and concentrations of ions present in these liquid media, two methods are discussed for the estimation of the double layer thickness and hence the product, necessary for the determination of the zeta potential () of the interface. Although both methods of calculation yield different values of, the results for the zeta potential are very similar in the regions of and characteristic of our systems. The application to the experimental data of three theoretical relations between electrophoretic mobility and zeta potential is also discussed. 相似文献
89.
A dynamics study [cross section and microscopic mechanism versus collision energy (E(T))] of the reaction O+ + H2 --> OH+ + H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E(T) = 0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E(T), and considering the influence of the collinear [OHH]+ absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies. 相似文献
90.
Modified samples of natural mordenites have been found to catalyze the oxidative condensation of methane to yield ethane and ethylene. The selectivity towards C2 hydrocarbons increases, whereas the acidity of zeolites falls.
, . C2 .相似文献