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101.
合成了两种新的聚醚取代的水杨醛亚胺Schiff碱锰(III)配合物MnL12Cl和MnL2Cl,研究了它们与表面活性剂2Brij35形成的金属胶束对BNPP的催化水解反应.探讨了催化反应机理,提出了水解反应的动力学数学模型;计算了催化反应的Michanelis常数和表观活化能,并与不含聚醚链的类似物MnL2Cl比较,考查了配合物配体中聚醚支链及其3端基对催化水解反应的影响.结果表明,催化水解反应遵循金属-氢氧离子机理;以羟基作为聚醚链端基的MnL12Cl的催化活性最高,在相同条件下,其表观一级速率常数约为MnL2Cl的3倍,为MnL2Cl的30倍.23 相似文献
102.
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104.
D. B. Tagiev P. S. Mamedova F. A. Abdullaeva M. K. Munshieva A. A. Turabova T. G. Takhirov 《Russian Chemical Bulletin》1992,41(11):2113-2115
The catalytic activity of Ni(II) bis-(5-thiopyrazol-4-aldiminates) was found to be related to the stereochemical flexibility of these compounds in the dimerization of propylene. The propylene conversion decreases with decreasing stereochemical flexibility of the complexes resulting from an increase in the bulk of the substituent at the coordinated nitrogen atom of the NiN2S2 chelate ring.Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaidjan, 370143 Baku. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2667–2670, November, 1992. 相似文献
105.
106.
Different copper/zirconium-yttrium catalysts have been tested in carbon black oxidation reaction. Supported mainly on differential thermal analysis and temperature programmed reduction, two different mechanisms have been proposed to explain the catalytic results. In the absence of copper, it has been shown that Zr3+ ions and associated anionic vacancies are responsible to the catalytic enhancement observed in the mixed oxides, oxygen species being activated on these sites. Among mixed zirconia-yttria solids, ZrO2-5 mol%Y2O3 is the most active catalyst. Copper impregnation on these oxides leads to the formation of different copper species. Small particles of CuO in low interaction with the support, induce a catalytic improvement due to the highest reducibility of these species. Moreover, in order to be more efficient, CuO species should have some interactions with the support, since impregnated samples are more active than the simple mechanical mixtures. 相似文献
107.
Hidetake Sakuraba Hiroshi Maekawa 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):41-45
The two modified β-cyclodextrin (β-CD) derivatives having catechol-type ligand (2,3- and 3,4-dihydroxy groups on the benzoate
ring) were synthesized. The chiral catalytic activity of their MoV and CuII complexes was examined in the asymmetric oxidation of aromatic sulfides using hydrogen peroxide in water (pH 6.0). The oxidation
with the MoV complexes of two β-CD derivatives were more accelerated than that with the CuII complexes. The sign of the optical rotation of the sulfoxides obtained in the above two cases showed the opposite configuration
in the oxidation of the same sulfide. The difference of the enantioselectivity appeared also between the two complexes of
the 2,3- and 3,4-dihydroxybenzoate derivatives with the same metal ion. While the use of the MoV complexes with the catechol derivatives yielded the sulfoxides with 35–65% ee, the use of the CuII complexes gave the products with the␣opposite configuration at 26–52% ee. The chiral induction in the oxidation, observed
conversely between the␣catalysts, was reflected on the chiral conformation of the respective metal catalysts, showed in Induced
Circular Dichroism (ICD) spectra. The highest optical yield, 65%, was observed in the oxidation of butyl phenyl sulfide using
the catalytic amount (0.1 equiv) of the MoV complex with mono-6-O-(3,4-dihydroxybenzoyl)-β-CD. The reaction gave predominantly the (S)-sulfoxide in 95% chemical yield. 相似文献
108.
Tadatomi Nishikubo Atsushi Kameyama Jun Yamashita Takahiro Fukumitsu Chika Maejima Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1011-1017
The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO2) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO2 proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc. 相似文献
109.
Ag/Al2O3选择性催化丙烯还原氮氧化物表面反应机理的原位红外光谱研究 总被引:2,自引:0,他引:2
在富氧条件下Ag/Al2O3对以丙烯为还原剂选择性催化还原NOx的反应有很高的催化活性.本实验成功地利用原位红外光谱分析手段,在真实的催化反应条件下,探讨了丙烯选择性还原NOx的反应机理,证实了催化剂表面反应中间体Al-NCO和Ag-NCO虽在真空中稳定,但在实际反应条件下极为活泼.催化剂表面上R-ONO和R-NO2分解成NCO是整个反应的速度控制步骤.这一结论与在真空系统条件下对其反应机理的研究结果一致,证明了在这一反应体系中两种研究方法的相关性.同时本实验还从反应机理上探讨了催化剂的水蒸气中毒现象.水蒸气的存在阻碍了催化剂表面R-ONO和R-NO2的生成,并进一步阻碍了反应的速度控
制步骤,即R-ONO和R-NO2向Al-NCO和Ag-NCO的转化,但这是一种完全可逆的暂时中毒现象.结合相应的催化剂活性评价结果对表面反应机理进行了讨论. 相似文献
110.
研究了PtCl^2^-6接着PVP修饰电极及其催化动力学,用循环伏安法考察了电极的电化学性质,结果表明在酸性溶液中对Fe^2^+的氧化有显著的催化作用。采用旋转圆盘电极法,极化曲线法等就电极对Fe^2^+氧化催化过程的控制步骤及有关动力学参数进行了测定。 相似文献