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151.
Nishizawa M Yadav VK Skwarczynski M Takao H Imagawa H Sugihara T 《Organic letters》2003,5(10):1609-1611
[reaction: see text] Hg(OTf)(2) exhibits remarkable catalytic activity for the hydroxylative cyclization of 1,6-enynes. The present procedure should involve a sequence of mercuration of a terminal alkyne, carbocyclization, hydration, and protodemercuration that regenerates the catalyst. 相似文献
152.
153.
Ichikawa S Tada M Iwasawa Y Ikariya T 《Chemical communications (Cambridge, England)》2005,(7):924-926
Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. 相似文献
154.
Linear propagation of two pulses through methanol solution of aluminum phthalocyanine chloride is investigated using a modified white-light Michelson interferometer. The observed coherence time of the white light is 6 fs, and the separation between the two-excitation pulses is set to about 10 fs. The excitation is dependent on the phase-relation between the two pulses. We have observed an enhancement of the excitation when the two pulses are in-phase and strong suppression of the excitation when the two pulses are out of phase by π. 相似文献
155.
Hydrogenation of cyclohexene with 0.1 mol% of the (nitrosyl)ruthenium catalyst [Cp∗Ru(NO)(C6H5)2] (1; Cp∗ = η5-C5(CH3)5) under 1.0 MPa of H2 in water at 90 °C for 13 h afforded cyclohexane in 94% yield. The nitrosyl-bridged dinuclear complex [Cp∗Ru(μ2-NO)2RuCp∗] (2) and the mononuclear cyclohexene complex [Cp∗Ru(NO)(η2-C6H10)] (3), which also serve as catalyst precursors, have been obtained from the reaction mixture. X-ray crystallographic analyses of 2 and 3 have revealed that the bridging nitrosyl ligands in 2 form an almost planar Ru2N2 four-membered ring with the Ru–Ru distance of 2.5366(5) Å, whereas the nitrosyl ligand in 3 is linear. On the other hand, a ruthenium complex without a nitrosyl ligand [Cp∗Ru(CH3CN)3][OSO2CF3] proved to be less effective for this hydrogenation. 相似文献
156.
We report the basis set dependencies and the basis set superposition errors for the hydrated complexes of K+ and Na+ ions in relation to the recent studies of the KcsA potassium channel. The basis set superposition errors are estimated by the geometry optimizations at the counterpoise-corrected B3LYP level. The counterpoise optimizations alter the hydration distances by about 0.02–0.03 Å. The enthalpies and free energies for K+ + n(H2O) → [K(H2O)n]+ and Na+ + n(H2O) → [Na(H2O)n]+ (n = 1–6) are compared between the theoretical and experimental values. The results show that the addition of diffuse functions to K, Na, and O species are effective. However, it is also found that the counterpoise corrections using diffuse functions work so as to underestimate the free energies for the complexes with increasing the hydration number. The stabilization energies in aqueous solution are larger for a Na+ ion than for a K+ ion, suggesting the contributions of their dehydration processes to the ion selectivity of the KcsA potassium channel. The changes in coordination distance between the isolated [K(H2O)8]+ and the [K(H2O)8]+ in the KcsA potassium channel indicate the importance of hydrogen bondings between the first hydration shell and the outer hydration shells. 相似文献
157.
158.
We discuss the scenario with TeV-scale right-handed neutrinos, which are accessible at future colliders, while holding down tiny seesaw-induced masses and sizable couplings to the standard-model particles. The signal with tri-lepton final states and large missing transverse energy is appropriate for studying collider signatures of the scenario with extra spatial dimensions. We show that the LHC experiment generally has a potential to discover the signs of extra dimensions and the origin of small neutrino masses. 相似文献
159.
Tadashi Suzuki Takao Miyazaki Nobuyoshi Natsuaki 《Applied Physics A: Materials Science & Processing》1990,50(3):265-267
The origin of the ion beam mixing effect, which causes the formation of smooth silicide films, is investigated for the Ti/Si solid-phase silicidation reaction. Ge ion beam mixing of a conventional Ti/c-Si structure with an oxide-contaminated interface shows an obvious effect when the implant conditions are such that the Ti/Si interface is amorphized. On the other hand, silicidation without ion mixing for Ti/a-Si and Ti/c-Si structures with oxide-free interfaces, prepared by sequential deposition in UHV, results in smooth and rough film surfaces, respectively. This strongly suggests that the ion beam mixing effect primarily comes from the amorphization of the Si substrate surface rather than the destruction of the interfacial oxide film. 相似文献
160.
The association constants, kd, of dichloroacetic acid (DCA) with ethers (tetrahydrofuran, tetrahydropyran, dibutyl ether, 1,4-dioxane) were measured in CCl4 from 20°–40° using near IR spectra. A linear relationship between log10KD and log10Kp was found, where Kp was the association constant of phenol with ethers. On the basis of their relationship the association constants of DCA with propylene oxide (PO) were estimated from those of phenol with PO. Furthermore, the ring-openings of PO with chloroacetic acids (trichloroacetic acid (TCA) or DCA) were studied kinetically in toluene. It was found that the PO-TCA reactions obeyed the second-order kinetics dependent on the first order both in the PO concn and in the TCA concn, and that the PO-DCA reactions obeyed the third-order kinetics on the first order in the PO concn and on the second order in the DCA concn. The elementary reaction rate constants were estimated on the basis of measured rate constants and estimated equilibrium constants and activation enthalpies were obtained from their temp dependence to be 13.5 in the PO-TCA reaction and 19.7 in the PO-DCA reaction. The mechanism was based on the activation enthalpy of elementary reaction and it was concluded that the main factor governing the reaction was the extent of activation of the protonated oxirane (the extent of polarization of the C-O bond in the oxirane ring). 相似文献