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双磷配体的合成及铑—双磷配体催化剂为混合辛烯氢甲酰化反应的催?… 总被引:2,自引:0,他引:2
合成了具有不同电子效应的3种双膦配体。其给电子性为Ph2P(CH2)4PPh2〉Ph2P(O)(CH2)4PPh2〉Ph2P(O)(CH2)4P(O)Ph2。这3种配体与醋酸铑二聚体配合物构成的催化剂,在混合辛烯的均相氢甲酰化反应中表现出的活性和选择性与配体给电子性强弱的次序完全相反。我们认为,具有弱配位性的「Rh(CH3COO)2」2Ph2P(O)(CH2)4P(O)Ph2催化体系,因其形成的活 相似文献
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许多化学工作者对单齿膦配体(PPh3,PBun3,PEt2Ph,P(OEt)3,P(OC6H5)3)与母体簇合物FeCo2(CO)9(μ3-S)的取代反应进行过详细研究[1-3],但对双齿膦配体与母体簇合物的取代反应研究报导较少.Aime[4]合成了含双齿膦配体的簇合物FeCo2(CO)7(μ3-S)(Ph2PCH2PPh2),并用13CNMR和IR光谱方法对其结构进行了表征.到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导.RosannaRossetti[2]通过研究母体簇合物与… 相似文献
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KI-醚类催化剂催化二氧化碳和环氧乙烷合成碳酸乙烯酯反应研究 总被引:7,自引:0,他引:7
合成了5个含有金属铁的环醚Fe(CO)3L(L1=Ph2P(CH2CH2O)2CH2CH2PPh2,L2=Ph2P(CH2CH2O)4CH2CH2PPh2,L3=OPh[(OCH2CH2)PPh2]2,L4=OPh[OCH2CH2)2PPh2]2)和[Fe(CO3)]2L5(L5=[Ph2PCH2CH2OCH2CH2PPh2]2).对它们进行了元素分析,并用红外光谱和核磁共振谱进行了结构表征.用KI+醚类为催化剂,催化二氧化碳与环氧乙烷反应生成碳酸乙烯酯,反应选择性大于96.9%.催化机理为碱催化,催化剂的活性受醚的影响.能和K+形成稳定配合物的醚可提高催化剂的活性.含金属铁的环醚和普通醚类相似,可以和钾离子作用,提高阴离子的亲核催化性能. 相似文献
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RuCl2(Ph3P)4或RuCl2(DMSO)4在甲苯中直接与等摩尔的亚胺膦配体N,N-双-[邻-(二苯基膦苯亚甲基)]乙二胺(P2N2)在甲苯中回流反应,高产率地合成了反式配位的双亚胺双膦钌配合物trans-RuCl2P2N2.在温和条件下,该配合物作为新型催化剂有效地催化α,β-不饱和酸和几种功能团烯烃的选择加氢反应.讨论了可能的催化活性物种. 相似文献
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含膦,氮配体的混合膦酸锆—钯催化剂的研制 总被引:9,自引:3,他引:6
用氯化二苯基膦为膦化试剂,首次对多乙烯多胺乙基膦酸-磷酸氢锆Zr(HPO4)1.35(O2PCH2CH2(NHCH2CH2)mNH2)0.65·H2O(ZP-PEPAEPA,n=0,1,2,3,4)载体表面进行二苯基膦化,合成了一类含膦氮配体的新型混合膦酸锆载体及负载钯催化剂。研究了有机膦酸侧链不同链长和Ph2PCl用量对配体载体制备的影响,并用IR,TG,DTG,DTA对这类载体及催化剂进行表征 相似文献
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顺丁烯二酸酐均相配位催化氢化反应研究 总被引:7,自引:0,他引:7
研究了在室温和大气压力下,几种过渡金属络合物对顺丁烯二酸酐氢化生成琥珀酸酐的催化活性,实验结果表明,它们的催化活性顺序是:PdCl2(PhCH2CN)2〉RuCl2(PPh3)3〉PdCl2(PhCN)2〉PdCl2(PPh3)2=RhCl(PPh3)2,在所应用的反应条件下,其中催化活性最高的络合物,PdCl2(PhCH2CN)2,给出了琥珀酸酐的产率高达93.0%。 相似文献
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(C5H4CH3)3Ho和(C5H4CH3)2Ho(C5H5)与5-本基四唑在THF中反应,得到了复合产物「(C5H4CH3)2HoN4CPh」2.「(C5H4CH3)(C5H5)HoN4CPh」2,该晶体属三斜晶系,P1空间群,晶胞参数为a=9.386(3),b=13.071(3),c=16.571(2)A,α=86.90(1),β=74.61(2),γ=77.30(2)°,V=1912.8(8 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