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991.
A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the
and
computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”. 相似文献
992.
笼形聚偕胺肟树脂的研究HX/ACAO树脂吸附贵金属 总被引:3,自引:0,他引:3
氢卤酸、硝酸、硫酸、磷酸和硼酸处理的笼形聚偕胺肟树脂(HX/A-CAO)对Ag+和等贵金属离子的吸附能力按如下顺序:PdCl42-:H3BO3/ACAO>BCAO>H3PO4/ACAO>HI/ACAO>H2SO4/ACAO>HCl/ACAO>HNO3/ACAO>HF/ACAO.IrCl62-:BCAO>H3PO4/ACAO>H3BO3/ACAO>HCl/ACAO>HF/ACAO>HI/ACAO>H2SO4/ACAO≥HNO3/ACAO.PtCl62:BCAO>H3BO3/ACAO>H2SO4/ACAO>HNO3/ACAO>HCl/ACAO>HF/ACAO>H3PO4/ACAO>HI/ACAO.Ag+:BCAO>H3BO3/ACAO>HI/ACAO>H2SO4/ACAO>HF/ACAO>HCl/ACAO>H3PO4/ACAO>HNO3/ACAO.AuCl4-:BCAO>H3BO3>H3PO4/ACAO>HF/ACAO>HCl/A-CAO>H2SO4/ACAO>HI/ACAO>HNO3/A-CAO.研究了H3BO3/ACAO树脂对Ag+和离子的吸附动力学,讨论了吸附机理. 相似文献
993.
Some new complexes between thecis-4,4′-dinitrodibenzo-18-crown-6 and rare earth chlorides LnCl3 (Ln=Nd, Gd, Yb) were synthesized in acetonitrile. Ligandcis-4,4′-dinitrodibenzo-18-crown-6 and its complexes were identified by infrared spectroscopy, X-ray diffraction and thermal
analysis (TG and DTA). Acis-trans isomerisation of the complexed ligand is observed about 148°C when heating the rare earth complex.
相似文献
994.
借助定量金相、扫描电子显微镜、透射电子显微镜等微观分析手段对钨质量分数为93%的钨合金在15~50GPa冲击压力下微观结构响应性态进行了考察,发现了一些钨合金所特有的现象,即钨颗粒与粘结相交界处出现成分迁移,新相析出;并结合断口分析,探讨了钨合金在冲击作用下发生断裂的微观特征与韧脆转化间的关系及其物理本质。 相似文献
995.
996.
The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units. 相似文献
997.
本文利用高压法制备HFe2Co(CO)9(μ3-S),作为原料,经脱质子化作用,再分别与(PPh3)2Cu(NO3)和PPh3AuCl反应,将Ph3Cu-或Ph3Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的化合物.文中对此两个新化合物进行了IR,UV,1H和31P NMR.元素分析、熔点测定等性质表征,并对(PPh3)2CuFe2Co(CO)7(μ3-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe2和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位. 相似文献
998.
H
0 and S
0 values of the complex formation in water of benzo-18-crown-6 (B18C6) with K+, Tl+, and Pb2+ were determined and compared with those of 18-crown-6. The H0 values of B18C6 are negative. The stability in water of the B18C6-metal ion complex at 25°C is governed largely by the magnitude of the H
0 value. The B18C6-metal ion complex is less stable in water than the corresponding 18C6-metal ion complex. This is due largely to a less favorable enthalpic contribution of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. The two aromatic ether oxygen atoms of B18C6 are responsible for the larger H
0 value of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. 相似文献
999.
Atactic polystyrene, both side group and main chain deuterated, was investigated by inelastic neutron scattering in a wide temperature range around the glass transition from 2 to 450 K. In the glass the Boson peak position is only very weakly influenced by the deuteration of the phenyl group. In the neighborhood of the glass transition temperatureT
g we find a fast relaxation process similar to other glasses. The onset of the fast relaxation in polystyrene, however, is observed already at temperaturesT
g — 200 K. Results from partially deuterated polystyrene suggest a change of the phenyl ring dynamics already far belowT
g. 相似文献
1000.
The water gas shift reaction (CO + H2O = CO2+ H2) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)5 and M(CO)6 (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)5 is first order in [Fe(CO)5], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)4Fe-CO2H]–. The water gas shift reactions using M(CO)6 as catalyst precursors are first order in [M(CO)6], inverse first order in [CO], and first order in [HCO2
–] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)5M-OCHO]–.The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)5 occurs at 110–140 °C. This reaction is second order in [Fe(CO)5], first order in [C2H4] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et3N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.The homogeneous photocatalytic decomposition of the formate ion to H2 and CO2 in the presence of Cr(CO)6 appears to be closely related to the water gas shift reaction. The rate of H2 production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)5 intermediate. Photolysis of the Cr(CO)6/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH2OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)6 at concentrations >0.004 mol L–1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)5
– intermediate by the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994. 相似文献