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Becke AD 《The Journal of chemical physics》2005,122(6):064101
Real-space models of nondynamical correlation between electrons of opposite spin and of parallel spin in multicenter (molecular) systems are discussed. These models are designed to be partnered with Hartree-Fock or exact Kohn-Sham exchange. Thus the numerous and well-known problems of local density-functional exchange-correlation approximations, especially in stretched odd-electron systems, are circumvented. 相似文献
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A new photoaldol route to alpha-amino-beta-hydroxy carboxylic acid esters is initiated by the photocycloaddition of aromatic or aliphatic aldehydes to 5-methoxyoxazoles. The 4-unsubstituted 5-methyloxazole 1 gave the cycloadducts 8a-f in high yields and excellent exo-diastereoselectivities. Hydrolysis of 8a-f gives the N-acetyl alpha-amino-beta-hydroxy esters 9a-f, which could be subsequently converted into the corresponding Z-didehydro alpha-amino acids 10a-f. Quartenary alpha-amino-beta-hydroxy esters 12, 14, 16, 18, and 20, which are stable against dehydration, were obtained from the 4-alkylated 5-methoxyoxazoles 2-6, in most cases highly erythro-selective due to the high degree of stereocontrol (exo) at the photocycloaddition (to give 11, 13, 15, 17, and 19) level. The relative configurations of the N-acetyl alpha-amino-beta-hydroxy esters were determined by NMR spectroscopy and comparison with chiral pool-derived compounds as well as by X-ray structure determination of the ester 23, formed by hydrolysis of the cycloadduct 22, derived from photocycloaddition of propionaldehyde to the isoleucine-derived oxazole 21. 相似文献
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The reaction behavior of NaN3, AgN3, and Me3SiN3 towards FNO2, CINO2, NO2SbF6, and NO2BF4 was investigated. At -30°C or below in a solvent-free system sodium azide did not react with CINO2, NO2BF4, or NO2SbF6. Below -30°C silver azide did not react either with neat C1NO2. Treatment of Me3SiN3 with pure C1NO2 led to the formation of C1N3, N2O, and Me3SiOSiMe3. A mechanism for this reaction has been proposed. Pure chlorine azide was isolated by fractional condensation and identified by its low-temperature Raman spectrum (liquid state). The reaction of Cp2Ti(N3)2 with C1NO2 also yielded C1N3 as the only azide-containing reaction product. Treatment of FNO2 with NaN3 at temperatures as low as -78°C always ended in an explosion which was probably due to the formation of FN3 as one of the reaction products. The reaction of NO2SbF6 with NaN3 in liquid CO2 (-55°C· T· -35°C) as the solvent afforded a new azide species which was stable at low temperature in solution only and was investigated by means of low-temperature Raman spectroscopy. The obtained vibrational data give strong evidence for the presence of tetranitrogen dioxide, N4O2, which can be regarded as nitryl azide (NO2N3). The structure and vibrational frequencies of N4O2 were computed ab initio at correlated level (MP2/6-31 + G*). In liquid xenon (-100°C· T· -60°C) NaN3 did not react with NO2SbF6. A previous literature report on the preparation of N4O2 could not be established. 相似文献
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Christoph Elschenbroich Fabian Gerson Hiroaki Ohya-Nishiguchi Christoph Wydler Axel Nissen 《Helvetica chimica acta》1977,60(8):2530-2538
Proton hyperfine data are reported for the radical anions of 1,8-di (propyn-1-yl)-naphthalene (I), 7,8,12,13-tetradehydro-10,11-dihydro-9H-cyclodeca[d,e]naphthalene (II) and 2,2′-di(propyn-1-yl)-biphenyl (III), as well as of 5,6,11,12-tetradehydro-7,8,9,10-tetrahydro-dibenzo[a,c]cyclodecene (IV) and its 8,8,9,9-tetradeuterio-derivative (IV-d4). The triple bonds in I and II can be regarded as roughly parallel, while those in IV (and IV-d4) may be considered as crossed. The π-spin distributions in I? to IV? are discussed in terms of simple MO models which suggest a weekly bonding interaction between the acetylenic fragments in IV?, in contrast to III? where such an effect appears to be negligible. The importance of an analogous interaction in I? and II? is difficult to deduce, since its inclusion into a MO model does not substantially affect the π-spin distribution in these radical anions. 相似文献
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Prof. Dr. Axel Reich 《Monatshefte für Mathematik》1982,93(1):33-37
A characterisation of all real Δ≠0 is given, such that $$\overline {f(\sigma + i\Delta \mathbb{N})} = \overline {f(\sigma + i\mathbb{R})} $$ holds for all Dirichlet seriesf(s)=Σa n n ?s and all σ greater than the abscissa of absolute convergence off. For only countably many Δ relation (*) is not valid. By using transcendental results it is shown, that (*) holds in the special case, Δ=1. 相似文献
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Marcia Araque-Marin Fabio Bellot Noronha Mickel Capron Franck Dumeignil Michle Friend Egon Heuson Ivaldo Itabaiana Jr. Louise Jalowiecki-Duhamel Benjamin Katryniok Axel Lfberg Sbastien Paul Robert Wojcieszak 《Molecules (Basel, Switzerland)》2022,27(12)
The development of the future French and European bioeconomies will involve developing new green chemical processes in which catalytic transformations are key. The VAALBIO team (valorization of alkanes and biomass) of the UCCS laboratory (Unité de Catalyse et Chimie du Solide) are working on various catalytic processes, either developing new catalysts and/or designing the whole catalytic processes. Our research is focused on both the fundamental and applied aspects of the processes. Through this review paper, we demonstrate the main topics developed by our team focusing mostly on oxygen- and hydrogen-related processes as well as on green hydrogen production and hybrid catalysis. The social impacts of the bioeconomy are also discussed applying the concept of the institutional compass. 相似文献
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