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161.
162.
Prof. Dr. Begoña García Dr. Francisco J. Hoyuelos Dr. Saturnino Ibeas Dr. María S. Muñoz Dr. Ana M. Navarro Dr. Indalecio A. Peñacoba Prof. Dr. José M. Leal 《化学:亚洲杂志》2010,5(12):2530-2540
The mechanisms for the hydrolysis of organopalladium complexes [Pd(CNN)R]BF4 (R=P(OPh)3, PPh3, and SC4H8) were investigated at 25 °C by using UV/Vis absorbance measurements in 10 % v/v ethanol/water mixtures containing different sulphuric acid concentrations in the 1.3–11.7 M range. In all cases, a biphasic behavior was observed with rate constants k1obs, which corresponds to the initial step of the hydrolysis reaction, and k2obs, where k1obs>k2obs. The plots of k1obs and k2obs versus sulfuric acid concentration suggest a change in the reaction mechanism. The change with respect to the k1obs value corresponds to 35 %, 2 %, and 99 % of the protonated complexes for R=PPh3, P(OPh)3, and SC4H8, respectively. Regarding k2obs, the change occurred in all cases at about 6.5 M H2SO4 and matched up with the results reported for the hydrolysis of the 2‐acetylpyridinephenylhydrazone (CNN) ligand. By using the excess acidity method, the mechanisms were elucidated by carefully looking at the variation of ki,obs (i=1,2) versus ${c_{{\rm{H}}^ + } }$ . The rate‐determining constants, k0,A‐1, k0,A‐2, and k0,A‐SE2 were evaluated in all cases. The R=P(OPh)3 complex was most reactive due to its π‐acid character, which favors the rupture of the trans nitrogen–palladium bond in the A‐2 mechanism and also that of the pyridine nitrogen–palladium bond in the A‐1 mechanism. The organometallic bond exerts no effect on the relative basicity of the complexes, which are strongly reliant on the substituent. 相似文献
163.
采用骤冷法对反应REBr3(s)+(3/2)Al2Br6(g)=REAl3Br12(g)进行研究,实验温度和压力范围分别是600~850 K和0.0077~0.22 MPa,反应平衡时间为6 h。测定它们在不同温度下的稳定常数。结果显示,中稀土的气态配合物稳定常数最大。以气态配合物REAl3Br12的lgKp与Z+/r作图,可将镧系稀土元素分为La-Eu,Eu-Er和Er-Lu三组,在每一组内,REAl3Br12的稳定常数均呈线性关系。在稀土气态配合物RE-Al3Br12稳定常数与原子序数及离子势(Z+/r)的变化关系中都存在着钆断现象。REAl3Br12稳定常数的对数值对RE(Ⅲ)的基态角量子数作图,得到四条直线,类似斜W效应。 相似文献
164.
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166.
Vasant R Choudhary Chinta Sivadinarayana Kshudiram Mantri 《Journal of Chemical Sciences》1999,111(5):669-676
The acidity and initial and time-on-stream activity in propane aromatization (at 550°C, space velocity of 3100 cm3g−1
(zeolite)h−1) of Ga-impregnated H-ZSM-5 zeolite without or with binders (50 wt%), such as silica, alumina and kaolin, have been investigated.
Both the acidity and catalytic activity of the zeolite are influenced by the presence of binder in the catalyst, depending
upon the binder. The influence is found to be lowest for alumina and highest for kaolin. Among the binders, alumina is the
most preferred binder for the zeolite catalyst. 相似文献
167.
S. Sugunan K. Sreejarani C.S. Deepa H. Suja 《Reaction Kinetics and Catalysis Letters》2000,71(2):307-311
A comparitive study of the acid-base properties and physico-chemical characteristics of pure SnO2, sulfated SnO2 and sulfated binary oxides of Sn and Pr was done. The data were correlated with the catalytic activity of the oxides towards benzoylation of toluene. 相似文献
168.
169.
R. V. Linko V. A. Soldatkina B. E. Zaitsev M. A. Ryabov V. I. Sokol 《Russian Chemical Bulletin》1999,48(6):1095-1099
Phenanthrenequinone monoxime and its mono-, di-, and trinitro derivatives were synthesized. The acidity constants and their
variation with the number and position of nitro groups were determined. The electronic and IR spectra of the nitro compounds
were studied. The bands in the electronic spectra were assigned based on quantum-chemical calculations in the Pariser—Parr—Pople
approximation. Correlations between the pK
a values and some calculated characteristics of the compounds under study were found.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1106–1110, June, 1999. 相似文献
170.