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新型YS类高分子铑配合物催化甲醇羰基化反应制备乙酸和乙酐 总被引:3,自引:0,他引:3
以含有两种不同配位原子的线型或交联大孔球型共聚物为配体的新型铑配合物,能在温和条件下催化甲醇羰基化为乙酸和乙酐.实验结果表明,这些新型共聚物铑配合物具有鳌合型顺-二羰基铑(Ⅰ)的结构特征,并有良好的热稳定性及高的催化活性和选择性. 相似文献
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顺二羰基铑(Ⅰ)共聚物催化剂的合成,结构与催化甲醇羰基化反应性能的研究 总被引:4,自引:0,他引:4
我们曾报道一系列含有两种不同配位基团的高分子共聚物与四羰基二氯二铑形成的顺二羰基铑(Ⅰ)配合物。这些配合物在催化甲醇羰基化反应中显示出高催化活性和高稳定性。本文采用4-乙烯吡啶(Y)和丙烯酸甲酯(B)共聚物为配体,对其与四羰基二氯二铑形成的配合物(YBRh)进行了表征。对该系列配合物催化甲醇羰基化生成乙酸的性能进行了评价。 相似文献
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螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨 总被引:4,自引:0,他引:4
螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨潘平来,柳忠阳,王晓筠,黄茂开,袁国卿(中国科学院化学研究所,北京100080)1引言甲醇在铑催化剂的作用下,与一氧化碳反应羰基化为乙酸,是一个重要的基本有机合成,反应。在为数众多的催化剂中,锗的配合物... 相似文献
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2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺的合成及其与铑(Ⅲ)的高灵敏显色反应的研究 总被引:1,自引:0,他引:1
合成了新显色剂2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺(5-I-PADMA),并研究了其与铑(Ⅲ)的显色反应。结果表明,在pH4.0~6.2的乙酸-乙酸钠缓冲介质中,铑(Ⅲ)与5-I-PADMA可形成稳定的1∶2配合物,该配合物呈现2个吸收峰,分别位于557、597 nm处。配合物形成后,以适量HClO4(0.24~5.57 mol.L-1)酸化,可转变为另一种具有较高吸收特性的质子化形体,其吸收峰分别红移至564、613 nm处。表观摩尔吸光系数达ε613=1.86×105L.mol-1.cm-1,铑的质量浓度在0~0.56 mg.L-1范围内符合比尔定律。该法是目前测定痕量铑的高灵敏显色体系之一,且具有良好的选择性。所建立的方法操作简单,应用于催化剂中微量铑的测定,结果满意。 相似文献
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羧酸铑(II)配合物是一类结构独特的同核双金属化合物,通常表现出较高的催化活性和选择性,中心金属铑、配体类型和空间结构都影响其催化性能。本文以三甲基乙酸铑(II)为母体,吡啶-2-基(吡啶-3-基)甲酮(23ma)和二吡啶-2-基甲酮(22ma)为轴向配体,设计合成了2种新型的三甲基乙酸铑(II)轴向配合物。通过1H NMR、13C NMR、 MS、 IR和X-单晶射线衍射对其结构进行表征,并测试了配合物对美罗培南类合成反应的催化性能。结果表明:与母体分子三甲基乙酸铑(II)相比,所合成的轴向配合物在美罗培南类合成体系中因存在溶解性较差等缺点,导致其催化性能均不佳。 相似文献
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The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted
indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator
model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was
established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing
analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997. 相似文献
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Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position. 相似文献
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The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations
were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples
were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of
hematite Fe2O3. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the
best fitting experimental data.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
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Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6. 相似文献
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微量钙的测定方法研究进展 总被引:5,自引:0,他引:5
介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。 相似文献
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Thermal behaviour of sodium oxo-salts of sulphur: Na2SO4, Na2S2O7, Na2S2O6, Na2SO3, Na2S2O5, Na2S2O4, Na2S2O3, Na2S3O6 and of sulphides Na2S and Na2S2 was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products
by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been
proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition
mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition
processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase
analysis. 相似文献
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Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared. 相似文献