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91.
An N-fused porphyrin rhenium complex was synthesized by the thermal reaction of an N-confused porphyrin with Re2(CO)10 and its structure was determined by X-ray crystallographic analysis. 相似文献
92.
[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions. 相似文献
93.
A. Fukumi I. Endo T. Horiguchi Y. Ishida T. Kondo T. Kuwamoto H. Matsuzaki T. Nakamura T. Takahashi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,42(4):243-249
Systematic study of hyperfine structures, Zeeman and Stark effects in Sm I is performed for the lowest 7G1-6 levels belonging to the configuration 4f 66s6p by atomic-beam laser spectroscopy with fluorescence detection. The hyperfine coupling constants of 7G2-6 levels are determined. From the Zeeman splittings for the 4f 66s 2 7F2-6 ? 4f 66s6p 7G2-6 transitions, g-values are determined for the 7G2.6 levels and the precision is improved by several orders of magnitude. From the Stark splittings for the 7F0-3 ? 7G1-3 transitions, tensor polarizabilities α 2(J) are determined for the upper 7G1-3 levels. Particularly for the 7G1 level (15 650.55 cm?1) which has close-lying opposite-parity level, the isotope dependence of α 2(J) is clearly observed for the first time. 相似文献
94.
Yoshiaki Hidaka Hiromitsu Masaoka Hidekazu Oshita Takuji Nakamura Koji Tanaka Hiroyuki Kawano 《国际化学动力学杂志》1992,24(10):871-885
The thermal decomposition of vinylacetylene (C4H4) was studied behind reflected shock waves using both a single-pulse method (reaction time between 0.8 and 3.3 ms) and a time-resolved UV-absorption method (230 nm). The studies were done over the temperature range of 1170–1690 K at the total pressure range of 1.3–2.3 atm. The mechanism was used to interpret both the early and late stages of vinylacetylene decomposition at the high temperatures. It was confirmed that C4H4 dissociation proceeded through the following three channels. The rate constant expression of reaction (1) was determined as k1 = 6.3 × 1013 exp(?87.1 kcal/RT) s?1. The rate constants of the succeeding reactions (chain reaction, C4H4 + H → i-C4H3 + H2 and C4H4 + H → C2H2 + C2H3 and decomposition reactions of free radicals, i-C4H3 + M → C4H2 + H + M) were confirmed or estimated. © John Wiley & Sons, Inc. 相似文献
95.
Travert A Nakamura H van Santen RA Cristol S Paul JF Payen E 《Journal of the American Chemical Society》2002,124(24):7084-7095
Hydrogen adsorption on Mo[bond]S, Co[bond]Mo[bond]S, and Ni[bond]Mo[bond]S (10 1 macro 0) surfaces has been modeled by means of periodic DFT calculations taking into account the gaseous surrounding of these catalysts in working conditions. On the stable Mo[bond]S surface, only six-fold coordinated Mo cations are present, whereas substitution by Co or Ni leads to the creation of stable coordinatively unsaturated sites. On the stable MoS(2) surface, hydrogen dissociation is always endothermic and presents a high activation barrier. On Co[bond]Mo[bond]S surfaces, the ability to dissociate H(2) depends on the nature of the metal atom and the sulfur coordination environment. As an adsorption center, Co strongly favors molecular hydrogen activation as compared to the Mo atoms. Co also increases the ability of its sulfur atom ligands to bind hydrogen. Investigation of surface acidity using ammonia as a probe molecule confirms the crucial role of sulfur basicity on hydrogen activation on these surfaces. As a result, Co[bond]Mo[bond]S surfaces present Co[bond]S sites for which the dissociation of hydrogen is exothermic and weakly activated. On Ni[bond]Mo[bond]S surfaces, Ni[bond]S pairs are not stable and do not provide for an efficient way for hydrogen activation. These theoretical results are in good agreement with recent experimental studies of H(2)[bond]D(2) exchange reactions. 相似文献
96.
A new strategy using a BINOL derivative as a chiral leaving group and Lewis acid has been developed for enantioselective alkylation of prochiral olefins. (R)-2,2'-Bis[2-(trimethylsilyl)ethoxymethyl]-1,1'-binaphthol is demonstrated to be an effective reagent for enantioselective hydroxymethylation of silyl enol ethers and trisubstituted alkenes. Electrophilic addition to prochiral olefins is accompanied by cleavage of an acetal that is dual activated by SnCl4 and the delta-effect of silicon through the S(N)2 substitution process. Enantioselective synthesis of cyclic terpenes is also described using this strategy. 相似文献
97.
Nakamura T Ikemoto JY Fujitsuka M Araki Y Ito O Takimiya K Aso Y Otsubo T 《The journal of physical chemistry. B》2005,109(30):14365-14374
The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB. 相似文献
98.
Isolation and structure determination of six glucocerebrosides from the starfish Luidia maculata 总被引:1,自引:0,他引:1
Two new glucocerebrosides, luidiacerebroside A (2) and B (6), were isolated from the cerebroside molecular species obtained from the less polar fraction of the CHCl3/MeOH extract of the starfish Luidia maculata using HPLC. Four known cerebrosides, CE-2b (1), astrocerebroside B (3), acanthacerebroside B (4), and CE-3-2 (5) have also been isolated and characterized. The structures of these cerebrosides were determined on the basis of chemical and spectroscopic evidence. Mass spectrometry of dimethyl disulfide derivatives was useful for the determination of the double-bond position in the long-chain base. 相似文献
99.
A kinetic study on methanol dehydrogenation over an FeTiZn0.44 alloy at 673 K suggested a mechanism including an adsorbed formaldehyde intermediate. A lower W/F and a higher methanol pressure favored a higher formaldehyde selectivity. 相似文献
100.