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101.
102.
The reactions of sterically protected phosphaalkenes with some boron reagents, such as boron hydrides, were carried out leading to hydroboration products depending on the substrates and boron reagents. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 187–196, 1999 相似文献
103.
Marcus Weck Alex R. Dunn Kozo Matsumoto Geoffrey W. Coates Emil B. Lobkovsky Robert H. Grubbs 《Angewandte Chemie (International ed. in English)》1999,38(18):2741-2745
A stabilization of the liquid-crystalline mesophase and thus an enlarged temperature range of the mesogenic phase is achieved by adding perfluorotriphenylene to a chiral liquid-crystalline triphenylene. This mesophase is based on 1:1 perfluoroarene–arene interactions (see picture). In a polymer with triphenylenes as mesogens in the side chains, the addition of perfluorotriphenylene led to crystallization. 相似文献
104.
Yuki?KanazawaEmail authorView authors OrcID profile Tetsuya?Yamada Aki?Kido Koji?Fujimoto Kyoko?Takakura Hiroaki?Hayashi Yasutaka?Fushimi Satoshi?Kozawa Koji?Koizumi Makiko?Okuni Naomi?Ueda Kaori?Togashi 《Applied magnetic resonance》2017,48(2):125-134
To visualize the condition of impregnation of polyethylene glycol (PEG) in waterlogged wood, we demonstrated magnetic transfer (MT) magnetic resonance imaging (MRI) through a series of process of PEG impregnation. Three different samples were examined; reference wood, 10 cm cut wood, and 5 cm cut wood. During this study, the upper section sample was kept immersed in water, for the middle and lower sections the concentration of PEG solution was changed at 20 wt% intervals from 20 to 100 wt%. The impregnated periods of each PEG solution concentration were 14 days. Then, MR imaging were performed with/without MT pulse. The MTR value for both 10 cm- and 5 cm-samples were shown to decrease at 20 wt% PEG at peak concentration. When the sample volume was large, e.g., 10 cm-sample, the MTR value decreased to 100 wt% PEG concentration. In contrast, when a sample volume was small, e.g., 5 cm-sample, MTR value decreased to 60 wt% PEG concentration. In conclusion, MTR analysis makes it possible to nondestructively visualize and evaluate the inner condition concerning the PEG impregnation method for waterlogged wood. 相似文献
105.
106.
In a melt with the base mol% composition 25Na2O-15B2O3-60SiO2, doped with chromium and manganese, a redox reaction takes place during cooling the melt. This reaction was studied using high temperature UV-vis spectroscopy. Above 600 °C, the reaction is in equilibrium and shifted during cooling to the Cr3+ and Mn3+ species. At temperatures between 500 and 600 °C, the kinetics of the redox reaction is decisive and the cooling rate plays an important part. At temperatures < 500 °C, the reaction is frozen in. The smaller the cooling rate, the smaller is the Cr6+ concentration and the lower is the fictive redox temperature.The kinetics of the reaction was described by a differential equation assuming Arrhenian behaviour. The equation was numerically solved and fictive temperatures were calculated. These temperatures depended on cooling rate similar to Bartenev equation. Activation energies calculated hereof were around 38 kJ?mol−1 larger than those inserted into the kinetic equation. The experimentally determined activation energy is 565 kJ?mol−1, a value much larger than the activation energies of diffusion of the polyvalent elements. The rate determining step in the case of the Cr3+/Cr6+/Mn2+/Mn3+ system is the electron transfer reaction, because a notable structural rearrangement is necessary during the course of the electron transfer reaction (Cr3+ and Cr6+ occur in octahedral and tetrahedral coordination, respectively). The latter leads to a large inner reorganisation energy and to an activation energy similar to that of the viscous flow. In the case of the redox reaction between copper and arsenic, the activation energy is much smaller (210 kJ?mol−1), because here the coordination numbers do not change during the course of the redox reaction. 相似文献
107.
Suzuki S Morita Y Fukui K Sato K Shiomi D Takui T Nakasuji K 《Journal of the American Chemical Society》2006,128(8):2530-2531
We have demonstrated the first MS and NMR observation of a face-to-face pi-bonded dimer of an organic radical (pancake-bonded dimer coined by R. S. Mulliken) in solution, using tri-tert-butylated phenalenyl radical 1, a 3-fold symmetric neutral hydrocarbon. In addition to the direct detection of the dimer signal by cold-spray ionization mass spectrometry (CSI-MS), 1H and 13C NMR spectra in solution gave definitive evidence of a well-defined D3d dimer structure with a 12-center-2-electron-long C-C bond formation, which is the same symmetry as seen in the crystalline state. On the basis of the NMR peaks of the dimer in the aromatic region (6.47 ppm for 1H NMR and 120-143 ppm for 13C NMR), we carried out nucleus-independent chemical shift (NICS) analysis, which showed that the ring center of the dimer became more aromatic (-7.1 ppm) than that of the monomer (-3.8 ppm). The trend of aromaticity generation was more pronounced in the interior of the dimer, which has been interpreted by the negative electron density induced in the bonding region as seen in the electrostatic potential surface. 相似文献
108.
109.
Fukumoto K Sakai A Oya T Nakazawa H 《Chemical communications (Cambridge, England)》2012,48(32):3809-3811
Desulfurization of N,N-dimethylthioformamide (Me(2)NCHS) by hydrosilane has been achieved under photo irradiation in the presence of a methyl iron complex. The reaction sequences have been proposed, in which silyl migration from Fe to S of thioformamide triggers the cleavage of a C=S bond to give a carbene-iron complex. This intermediate was isolated and characterized by X-ray analysis. 相似文献
110.
Integral equation theory for molecular liquids is one of the powerful frameworks to evaluate solvation free energy (SFE). Different from molecular simulation methods, the theory computes SFE in an analytical manner. In particular, the correction method proposed by Kovalenko and Hirata [Chem. Phys. Lett. 290, 237 (1998); and J. Chem. Phys. 113, 2793 (2000)] is quite efficient in the accurate evaluation of SFE. However, the application has been limited to aqueous solution systems. In the present study, an improved method is proposed that is applicable to a wide range of solution systems. The SFE of a variety of solute molecules in chloroform and benzene solvents is evaluated. A key is the adequate treatment of excluded volume in SFE calculation. By utilizing the information of chemical bonds in the solvent molecule, the accurate computation of SFE is achieved. 相似文献