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71.
A mechanistic study on the Nieuwland catalysis for dimerization of acetylene is performed by detecting copper–acetylene and copper–monovinylacetylene π‐complexes and also by examining the kinetics under virtually the same reaction conditions employed in the industrial process. An efficient H/D exchange occurs between acetylene and protons in the Nieuwland catalytic system. Addition of a coordinating ligand to the conventional Nieuwland catalytic system results in improvement of the catalytic activity and selectivity for the acetylene dimerization. The kinetic analysis including the kinetic deuterium isotope effect provides valuable insight into the Nieuwland catalytic mechanism of the dimerization of acetylene. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
72.
Ayumi Ishii Shinobu Kishi Hideki Ohtsu Toshifumi Iimori Takakazu Nakabayashi Nobuhiro Ohta Naoto Tamai Milan Melnik Miki Hasegawa Yuzo Shigesato 《Chemphyschem》2007,8(9):1345-1351
The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand. 相似文献
73.
Kun‐Heng Chiang Shi‐Han Lu Wan‐Ping Yen Naoto Uramaru Wei‐Siou Tseng Te‐Wei Chang Fung Fuh Wong 《Heteroatom Chemistry》2016,27(4):235-242
A convenient synthetic method for N‐arylformamide derivatives was successfully developed by reacting α‐iodo‐N‐arylacetamides with formamide. This method was applicable to α‐iodo‐N‐arylacetamide substrates bearing electron‐donating or electron‐withdrawing groups, N‐(benzo[d][1,3]dioxol‐5‐yl)‐2‐iodoacetamide, 2‐iodo‐N‐(pyridin‐2‐yl)acetamide, and 2‐iodo‐N‐(naphthalen‐4‐yl)acetamide to give the corresponding N‐arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation. 相似文献
74.
Takahiro Matsumoto Seikou Nakamura Naoto Kojima Tomohiro Hasei Masayuki Yamashita Tetsushi Watanabe Hisashi Matsuda 《Tetrahedron letters》2017,58(36):3574-3578
From the methanolic extract of the aerial parts of Isodon japonicus, two new ent-kaurane diterpenes, isodonterpenes I and II, were isolated together with 10 known diterpenes. Their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The absolute configuration of isodonterpene I was elucidated by Cu-Kα X-ray crystallographic analysis. Antimutagenic activities of the major diterpenes were evaluated by the Ames test. This study represents the first evaluation of the antimutagenic activities of ent-kaurane diterpenes. 相似文献
75.
Ni-catalyzed hydrosilylative cyclization of difluoro-substituted 1,6-enynes can be carried out. The presence of a geminal-difluoromethylene group at an alkene terminus in enynes is essential for the reaction to proceed. 相似文献
76.
Takamitsu Otake Yoshie Aoyagi Takashi Yarita Masahiko Numata 《Analytical and bioanalytical chemistry》2010,397(6):2569-2577
Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine
pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial
Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay,
and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by γ-irradiation. This sample is in
the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using
multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization
to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and
PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p′-DDE, p,p′-DDT, and p,p′-DDD) were 1.05–14.0 μg kg−1 and 1.57–18.0 μg kg−1 for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution
mass spectrometry. 相似文献
77.
Takenaka S Susuki N Miyamoto H Tanabe E Matsune H Kishida M 《Chemical communications (Cambridge, England)》2010,46(47):8950-8952
Pd cathode catalysts for polymer electrolyte fuel cells have been covered with silica layers a few nanometres thick. The silica-coated Pd catalysts showed high activity and excellent durability for the oxygen reduction under the severe cathode conditions of PEFCs, while Pd catalysts without silica-coating were seriously deactivated under the same conditions. The coverage of Pd metal with silica prevents the diffusion of Pd species out of the silica layers. 相似文献
78.
Hiroyuki Okamura Hiroki SakaeKeiji Kidani Naoki HirayamaNoboru Aoyagi Takumi SaitoKojiro Shimojo Hirochika NaganawaHisanori Imura 《Polyhedron》2012,31(1):748-753
The extraction constant and the two-phase stability constant (KD,Mβ3) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][Tf2N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and [C4mim][Tf2N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (KD,M) of the neutral Eu(III) chelate because the [C4mim][Tf2N] system gave the high KD,Mβ3 value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu3+ in the neutral Eu(III) chelate in [C4mim][Tf2N] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III) chelate extracted but also Eu(tta)3(H2O)3 synthesized as a solid crystal were almost completely dehydrated in [C4mim][Tf2N] saturated with water. Consequently, the higher KD,M or extractability of the neutral Eu(III) chelate in the [C4mim][Tf2N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C4mim][Tf2N] molecules. 相似文献
79.