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1.
N. Hamamoto J. Jitsukawa C. Satoko 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,19(2):211-221
First-principle electronic structure calculations are carried out for MxC 60 q , where M = Li, Na, K and ( x , q ) = (1, 0),(1,±1),(2, 0),(3, - 1),(6, 0),(6, - 1),(12, 0) using the local density functional. The electric dipole moment for MC60 agrees with the experimental results. The calculated Mulliken charge indicates that the bonding of the alkali atom with C60 is mostly ionic except for lithium. The alkali atom prefers to make many bonds with the carbon atoms rather than a single bond with the neighbor carbon atom. The calculated adsorption energy suggest that the metal-metal bonding of sodiums and potassiums on C60 arises for more than the six valence electrons in the alkali atoms. The lithium-lithium bond is, on the other hand, not appeared for x ? 12. The difference in the most stable geometry between lithiums and the other alkali atoms on C60 comes from the covalent character of the lithium-carbon bond. 相似文献
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Fumie Takei Daisuke Kodama Sugiko Nakamura Kiyotaka Onitsuka Shigetoshi Takahashi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):585-595
Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006 相似文献
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Treatment of 3,4-alkadienyl carbonates 2a-i with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), readily generated by the reaction of Ti(O-i-Pr)(4) with 2 i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford vinyltitanium compounds 3 which, in turn, reacted with H(3)O(+), D(2)O, or iodine to give alpha-substituted beta,gamma-unsaturated esters 4 in good to excellent yields. The olefin moiety of the hydrolysis product 4 has (Z)-geometry mainly except for 4h. Starting from chiral 2f or 2g, the reaction proceeded stereospecifically to give optically active alpha-substituted beta,gamma-unsaturated ester 4f or 4g having (Z)-olefin geometry exclusively. 相似文献
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Toshio Yamanaka Mitsuru Ohkubo Fumie Takahashi Masayuki Kato 《Tetrahedron letters》2004,45(13):2843-2845
An efficient synthesis of the orally-active GpIIb/IIIa antagonist FR184764 was achieved. The key intermediate, an optically active ethynyl β-amino ester, was synthesized efficiently by utilizing a lipase catalyzed kinetic resolution step. 相似文献
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The reaction of 2-functionalized 1-halo-2,n-enynes (n = 7 or 8) with a divalent titanium reagent, Ti(O-i-Pr)4/2i-PrMgCl, proceeded in a domino fashion to afford bicyclic compounds in good yields. 相似文献
7.
Wada A Ogo S Nagatomo S Kitagawa T Watanabe Y Jitsukawa K Masuda H 《Inorganic chemistry》2002,41(4):616-618
The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H(2)bppa)(OOH)](2+) (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H(2)bppa)(HCOO)](ClO(4))(2) with H(2)O(2) in acetone at -50 degrees C gave characteristic UV-vis (lambda(max) = 568 nm, epsilon = 1200 M(-1) cm(-1)), ESR (g = 7.54, 5.78, and 4.25, S = (5)/(2)), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)](2+)), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d(6)-acetone revealed two intense bands at 621 and 830 cm(-1), which shifted to 599 and 813 cm(-1), respectively, when reacted with (18)O-labeled H(2)O(2). Reactions of the isolated (bppa)Fe(III)-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H(2)bppa)Fe(III)-O*]. 相似文献
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1,2,4,5-Tetraalkylidene- and 1,4-dialkylidenecyclohexanes were prepared by the regio- and stereoselective homocoupling of skip-type diynes and enynes, and their Diels-Alder reaction to form a polycyclic compound was demonstrated. 相似文献