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101.
Synthesis of camphor derived chiral allenes and their hydroboration-oxidation reactions are described. Reaction of (1R)-(+)-camphor with alkynyllithium followed by the reduction of the resulted propargyl alcohol derivatives using AlH3 furnished chiral allenes 2a-g in excellent yields with high diastereoselectivity. Reduction of the propargyl alcohols with aluminum hydride proceeded through selective intermolecular anti-addition of hydride ion. The stereochemistry of the chiral allenes 2 was assigned based on lanthanide shift studies and chemical correlations. Diastereoselectivity was observed in the hydroboration-oxidation of 2 which produced a mixture of (E,R) and (E,S) stereoisomers in a ratio of 6:1 to 18:1. 相似文献
102.
Summary Three novel heterotrinuclear complexes have been prepared, [Cu2(oxdn)2Zn](ClO4)2 (1) and [Cu2(oxdn)2-M(H2O)2](ClO4)2 with M=Mn (2) and Co (3) [oxdn-oxamidobis (propionato)], and characterized by spectral data. The temperature dependence of the magnetic susceptibilities of (2) and (3) has been studied in the 4–300K range, and the exchange integrals J=–20.90cm–1 for (2) and J=–62.36cm–1 for (3) calculated. These results are commensurate with antiferromagnetic interactions between the adjacent metal ions. 相似文献
103.
Yan Ouyang Wei Zhang Yue Ma Na Xu Dai-Zheng Liao Kazuyoshi Yoshimura Shi-Ping Yan 《Structural chemistry》2007,18(6):891-898
Two new tetranuclear complexes of macrocyclic oxamide [Cd(CuL)3](NO3)2·2.5H2O 1, [Mn(CuL)3(OH)2](ClO4)2·Mn(H2O)6·4.5H2O 2 (L = 1,4,8,11-tatraazacyclotradecanne-2,3-dione) have been synthesized, structurally characterized and preliminary investigated
by magnetic studies. The structures of the title complexes consist of a tetranuclear units MCu3 (M = Cd, Mn), the packing diagram shows two-dimensional and three-dimensional system through intermolecular weak interactions.
The temperature-dependent magnetic susceptibilities of complex 2 were analyzed by an approximate treatment leading to J = −33 cm−1, gCu = 2.10, gMn = 1.95 indicating antiferromagnetic exchange between Cu(II) and Mn(II) ions. 相似文献
104.
A new potential tetradentate ligand, 1,4-bis(N-1-methylimidazol-2-ylmethyl)-1,4-diazacycloheptane (l), together with its CuII complex [CulCl]ClO4 (1), has been reported. The crystal structure of 1, determined by single-crystal X-ray analysis, shows that it is in chiral P212121 space group. The CuII centre is penta-coordinated in square pyramidal geometry and the diazacycloheptane (DACH) ring adopts normal boat configuration. The most striking feature of this complex is the formation of a 3D network bridged through the C-H?Cl hydrogen bonds with the perchlorate anions in the cavities, and stabilized via π-π stacking interactions along the a-direction. The solution behaviour of 1 has been further investigated by UV/Vis and ESR techniques. 相似文献
105.
106.
La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用 总被引:14,自引:0,他引:14
我国将稀土作为助剂引入镍基甲烷化催化剂,大大提高了催化剂的活性和热稳定性,并已投入工业应用[1-3].稀土对不同镍催化剂反应性能及其作用机理的研究已有一些报导[3-7].谢有畅等观察到镍负载在经单层La2O3改性的γ-Al2O3表面,其晶粒要比没有La2O3时小得多.Rotgerink等认为添加La后反应速率的增加不只是由于几何效应,而是La对甲烷化本身有促进作用,单位镍表面的活性是随La含量不同而改变的,活性增加的同时表观活化能也增加[5].作为助剂的La2O3在氢还原和反应过程中的变化及其作用的研究和讨论较少,目前一般认为添… 相似文献
107.
An enantiospecific synthesis of Schinzer's ketone 3 from (R)-(+)-pulegone via alpha-carbonyl radical cyclization was accomplished. This work also constitutes an enantiospecific formal syntheses of (-)-pinguisenol and (-)-alpha-pinguisene. The intermediate ketone 4 would be useful for the synthesis of other pinguisane-type sesquiterpenes. 相似文献
108.
This
study discussed the phenomena on thermal polymerization of α-methylstyrene
(AMS). A curve scanned by temperature-programmed technique was performed by
differential scanning calorimetry (DSC). Heat of polymerization (ΔH) and onset temperature of exothermic (T0) behavior were determined
to be 280±10 J g-1 and about 138±1°C,
respectively. A dimer formation mechanism was proposed for initiation of the
propagating chain. Spectroscopic identification of dimer structure was conducted
by infrared (IR) spectroscopy in the wavenumber from 650 to 1100 cm-1associated
with molecular fingerprint characteristics. The mechanism of thermal polymerization
on α-methylstyrene proposed in this study was similar to that of styrene
suggested by Mayo. 相似文献
109.
The thermal decomposition of ammonium vanadyl oxalate supported on La2O3, MgO, SiO2, Al2O3, ZrO2, TiO2, SAPO-5, and ZSM-5 oxides in a dynamic atmosphere of dry air was compared by thermal gravimetric analysis (TG) and differential thermal analysis (DTA). The calcined catalysts were characterized by X-ray diffractometry (XRD). The TG and DTA results demonstrate that the surface acid-base properties of the oxides play a significant role in the decomposition behaviour of the supported ammonium vanadyl oxalate, i.e. the basic oxides exhibit an endothermic effect and the acidic oxides show an exothermic effect. Two mechanisms are suggested for thermal decomposition of ammonium vanadyl oxalate on basic and acidic oxides, respectively. After transformation of the ammonium vanadyl oxalate to vanadia, subsequent rearrangement of the vanadia on the surface of the supports was also observed. During the thermal treatment or calcination in air, solid state reactions of vanadia with the surface of oxides such as La2O3, ZrO2 and TiO2 took place to form new phases. 相似文献
110.
This research applies semiconductor photocatalysts, which are formed by metal ion exchange on the surface of kaolinite catalyst with cations, to the study of photocatalytic degradation of 4‐chlorophenol. The analysis results of catalyst properties shows that, after sintering at 400 °C, kaolinite catalyst has a particle size of between 10–100 nm indicating the nano level of synthesized catalysts. Under the same condition, kaolinite‐Ag/Zn catalyst works better in degradation efficiency than single kaolinite‐Ag and kaolinite‐Zn catalysts. Kaolinite‐Zn catalyst declines in degradation efficacy after 150 minutes and performs poorer than the other three types of kaolinite catalysts. In the experiments of different amounts of catalysts, when the concentration exceeds 0.1 wt%, utilization of light energy and degradation efficiency will be reduced due to shielding effect. When at different pH values, the higher the pH value, the more OH‐will be released and that is beneficial for reaction with substances and the increase of reaction rate. Finally multivariate analysis proves that there is one determining factor that influences the photocatalytic degradation of 4‐chlorophenol in kaolinite catalysts, named as “the factor with intermediates competition degree,” the one affecting the 4‐CP degradation at different weight percentages that is referred to as the “shielding effect factor.” 相似文献