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101.
Roy E. Hoffman Noach Treitel Mordecai Rabinovitz 《Magnetic resonance in chemistry : MRC》2001,39(8):489-494
Isotope shifts are a well-established tool for structural analysis by NMR. The substitution of a protium with a deuterium is the most widely studied of these effects. However, such studies call for specific deuteration that requires complex synthetic techniques owing to the low natural abundance of deuterium. 13C occurs at a higher natural abundance and couples strongly with its attached proton. We have developed and refined a method to reliably observe these much smaller shifts without needing to resort to chemical synthesis. We show that carbon induced isotope shifts reflect structural features. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
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104.
Bridgeman AJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2935-2941
The structures and vibrational frequencies of the alpha- and beta-isomers of the phosphomolybdate Keggin anion [PMo(12)O(40)](3-) have been calculated by using density functional theory. Good agreement between the calculated unscaled vibrational frequencies and those determined experimentally and between the calculated and observed IR traces has been obtained allowing the IR and Raman spectra to be assigned. For the alpha-isomer, the agreement with experiment using the current level of theory is superior to that obtained previously. For the beta-isomer, for which no non-empirical study has previously been reported, the agreement with experiment is slightly poorer but still allows the spectrum to be assigned unambiguously. To calculate the structure and vibrational spectra of these large molydate cluster ions requires large basis sets and a good treatment of electron correlation and relativistic effects. For the 53-atom [PMo(12)O(40)](3-) ions, the computational demands are very high, requiring several months computational time. The calculated IR spectral traces for the two isomers are quite similar due to the relative flexibility of the molybdates, where the slight weakening of the bonding of the rotated trimetallic unit to the rest of the cluster in the beta-isomer is compensated by contraction of the bonds within the unit, and the structure of the [MO(6)] and [PO(4)] units in the two isomers is nearly identical. The vibrations characteristic of the bridging Mo-O-Mo bonds involve both the "2-2" junctions between rotated [M(3)O(13)] units and the "1-2" junctions between rotated and unrotated units. The separation of "ligand" and "interligand" vibrations is not clear. The vibrational analyses confirm the high symmetry, namely T(d) and C(3v) for the alpha- and beta-isomers, respectively, assumed by previous workers in this field. The characteristic group frequencies for the Type I polyoxometalates containing both edge- and corner-sharing I octahedra have been identified. 相似文献
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107.
Bulgakov R. G. Akhmadieva R. G. Musavirova A. S. Golikova M. T. 《Russian Chemical Bulletin》2001,50(4):731-733
Chemiluminescence (max = 790 nm) in the oxidation of fulleride Na2C60 by the (NH4)2Ce(NO3)6 complex in THF was found. The 3C60* triplet of fullerene formed in the transfer of an electron from the intermediate C60
– anion to CeIV was suggested to be the chemiluminescence emitter. 相似文献
108.
烷基硫酸盐表面张力的量子化学研究 总被引:1,自引:0,他引:1
用AMl量子化学计算法优化了十三烷基硫酸根阴离子和——CH3在不同取代位的十二烷基硫酸根阴离子的几何构型,得到最优构型时最高占据分子轨道能级EHOMO、最低空轨道能级ELUMO、电子能量Eele和偶极矩μ等数据.将这些电子结构数据分别与表面张力相拟合,得到很好的相关性。文中讨论了——CH3在不同位置取代对表面张力的影响。 相似文献
109.
Toralf Peymann Axel Herzog Carolyn B. Knobler M. Frederick Hawthorne 《Angewandte Chemie (International ed. in English)》1999,38(8):1061-1064
No explosion , but per-B-hydroxylation occurs if the icosahedral boron hydrides [closo-B12H12]2− (see picture), [closo-CB11H12]−, or closo-1,12-(CH2OH)2-1,12-C2B10H10 are refluxed in 30 % hydrogen peroxide. Thus, the three isoelectronic species [closo-B12(OH)12]2−, [closo-1-H-1-CB11(OH)11]−, and closo-1,12-H2-1,12-C2B10(OH)10 were obtained. ○=BH, ○=BOH. 相似文献
110.
Köchner T Engesser TA Scherer H Plattner DA Steffani A Krossing I 《Angewandte Chemie (International ed. in English)》2012,51(26):6529-6531
Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P(9)](+) was prepared using a combination of the oxidant [NO](+) and weakly coordinating anion, [Al{OC(CF(3))(3)}(4)](-). [P(9)](+) consists of two P(5) cages linked by a phosphonium atom to give a D(2d)-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure. 相似文献