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61.
The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO2Me) by Cp2TaH3 and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η2-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η2-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc. 相似文献
62.
Kalina Mambourg Laurie Bodart Nikolay Tumanov Steve Lanners Johan Wouters 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(3):205-211
The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C21H18N2O2S2·0.463CH3OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol?1 between the two conformers. 相似文献
63.
The(3+1)-dimensional Burgers equation, which describes nonlinear waves in turbulence and the interface dynamics,is considered. Two types of semi-rational solutions, namely, the lump–kink solution and the lump–two kinks solution, are constructed from the quadratic function ansatz. Some interesting features of interactions between lumps and other solitons are revealed analytically and shown graphically, such as fusion and fission processes. 相似文献
64.
Chang-Chun Ding Shao-Yi Wu Li-Juan Zhang Si-Ying Zhong Xiao-Hong Chen 《Molecular physics》2020,118(3)
Metal organic frameworks (MOFs) have been well-known and extensively researched due to the high storage /good selectivity for gas molecules. Herein, the structures and electron paramagnetic resonance (EPR) spectra for dicopper paddle wheel MOF compound (Cu2(µ2-O2CCH3)4 with various gas molecule are theoretically investigated by density functional theory (DFT) calculations. The adsorption energies and isotherms (including pure gas molecules and the mixed ones) are calculated for the gas molecules interacting with the unsaturated Cu2(µ2-O2CCH3)4. Both quantities exhibit the roughly consistent orders (e.g. H2S?>?NH3?>?CO2?>?CO?>?H2O?>?N2?>?NO?>?H2 for isotherms and H2S?>?NH3?>?N2?>?CO2?>?NO?>?H2O?>?H2?>?CO for adsorption energies), possibly suggesting that this material may act as a potential adsorbent of these gas molecules. The catalytic property of Cu2(µ2-O2CCH3)4 for oxidation of CO and NO into non-toxic molecules and splitting of H2O into H2 and O2 in the solvent condition are uniformly discussed. Simulation of Grand Canonical Monte Carlo (GCMC) in MS 8.0 and calculations in Langmuir model reveal that Cu2(µ2-O2CCH3)4 has good selectivity for CH4 in natural gas (CH4/CO2/N2) and SO2 in fog (SO2/NO/NO2/H2O/O2), which would exhibit potential environmentally friendly applications. 相似文献
65.
66.
Based on the surface passivation of n-type silicon in a silicon drift detector(SDD), we propose a new passivation structure of SiO2/Al2O3/SiO2 passivation stacks. Since the SiO2 formed by the nitric-acid-oxidation-of-silicon(NAOS)method has good compactness and simple process, the first layer film is formed by the NAOS method. The Al2O3 film is also introduced into the passivation stacks owing to exceptional advantages such as good interface characteristic and simple process. In addition, for requirements of thickness and deposition temperature, the third layer of the SiO2 film is deposited by plasma enhanced chemical vapor deposition(PECVD). The deposition of the SiO2 film by PECVD is a low-temperature process and has a high deposition rate, which causes little damage to the device and makes the SiO2 film very suitable for serving as the third passivation layer. The passivation approach of stacks can saturate dangling bonds at the interface between stacks and the silicon substrate, and provide positive charge to optimize the field passivation of the n-type substrate.The passivation method ultimately achieves a good combination of chemical and field passivations. Experimental results show that with the passivation structure of SiO2/Al2O3/SiO2, the final minority carrier lifetime reaches 5223 μs at injection of 5×1015 cm-3. When it is applied to the passivation of SDD, the leakage current is reduced to the order of nA. 相似文献
67.
声发射技术作为一种动态无损检测手段,主要实现对材料产生的缺陷进行动态监测及损伤位置的预测。微机电系统声发射传感器在检测材料疲劳裂纹位置和扩展方向上应用广泛,实现其对材料裂纹的3-D动态位移检测,对于无损检测技术的发展具有重要意义。该文提出了一种新型3-D微机电系统声发射传感器,首先对3-D微机电系统声发射传感器进行了结构设计和性能分析,结构方面主要包括z方向响应传感单元和x、y方向响应传感单元设计;其次通过传感器的阻尼、谐振点处灵敏度计算,证明传感器的性能良好;最后采用有限元软件ANSYS对z方向响应传感单元做了模态和谐响应分析,x、y方向响应传感单元做了模态分析和谐响应分析,仿真结果与理论值吻合较好,验证了结构设计的合理性,对实现材料裂纹的三维动态检测具有一定的参考意义。 相似文献
68.
69.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones 下载免费PDF全文
Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
70.
Yaogang Hu Peng Teng Wenyang Gao Xiaobing Zuo Lukasz Wojtas Randy W. Larsen Shengqian Ma Jianfeng Cai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2501-2507
Foldamers offer an attractive opportunity for the design of novel molecules that mimic the structures and functions of proteins and enzymes including biocatalysis and biomolecular recognition. Herein we report a new class of nonnatural helical sulfono‐γ‐AApeptide foldamers of varying lengths. The crystal structure of the sulfono‐γ‐AApeptide monomer S6 illustrates the intrinsic folding propensity of sulfono‐γ‐AApeptides, which likely originates from the bulkiness of tertiary sulfonamide moiety. The two‐dimensional solution NMR spectroscopy data for the longest sequence S1 demonstrates a 10/16 right‐handed helical structure. Optical analysis using circular dichroism further supports well‐ defined helical conformation of sulfono‐γ‐AApeptides in solution containing as few as five building blocks. Future development of sulfono‐γ‐AApeptides may lead to new foldamers with discrete functions, enabling expanded application in chemical biology and biomedical sciences. 相似文献