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"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons. 相似文献
45.
S. Patzer N.L. Arthur P. Potzinger H.Gg. Wagner 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):2543-227
The photolysis of Me6Si2 at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me3SiH elimination with the concomitant formation of Me2SiCH2 with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10−3, which results in the formation of Me4Si and Me2Si. The main fate of the excited Me6Si2 molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me3Si and Me2SiCH2, are the same as those found in the photolysis of Me4Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33). 相似文献
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A. Mandelis W. Lo R. E. Wagner 《Applied Physics A: Materials Science & Processing》1987,43(2):123-130
The electrical and dielectric properties of mercuric iodide were studied at room temperature under various intensities and colours of light in the frequency range 1 Hz–10 kHz. In the high-frequency region (>40 Hz), the real part of the dielectric constant () is almost constant with frequency (f), colour and intensity of light. At lower frequencies, varies nearly as 1/f and monotonically increases with intensity (I) of the yellow (or green) light, whereas it is almost constant with red light intensity. This behaviour is discussed in the view of the different polarization contributions. The imaginary part of the dielectric constant () was found to vary as 1/f over the frequency range studied. This behaviour was observed whether the crystal was in dark or illuminated implying that the roomtemperature ac dark- or photo-conductivity () is independent of frequency. The observed variation of with intensity of yellow (or green) light was found to follow anI
1/2 dependence and a weaker dependence for the red light. the red light. The conductivity behaviour is discussed in the view of the current theories. 相似文献
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Wagner F Gruber O Lackner K Murmann HD Speth E Becker G Bosch HS Brocken H Cattanei G Dorst D Eberhagen A Elsner A Erckmann V Fussmann G Gehre O Gernhardt J Gierke Gv Glock E Grieger G Grigull P Haas G Hacker H Hartfuss HJ Jäckel H Jaenicke R Janeschitz G Junker J Karger F Kasparek W Keilhacker M Kick M Klüber O Kornherr M Kroiss H Kuehner M Lenoci M Lisitano G Maassberg M Mahn C Marlier S Mayer HM McCormick K Meisel D Mertens V Müller ER Müller Müller G Niedermeyer H Ohlendorf W 《Physical review letters》1986,56(20):2187-2190
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(2S,4S)-2-(tert-Butyl)-5-oxo-1,3-dioxolan-4-acetic acid ( 1 ) was dilithiated to the enolate 2 in toluene and THF with lithium diisopropylamide (LiN(i-Pr)2) under various conditions. Deuteration experiments with 2 showed that two different stable forms of the enolate could be produced, depending on whether the deprotonation of 1 had been carried out in toluene or THF. The generated (i-Pr)2NH was coordinated to the enolate and, hence, served as a strong lipophilic solvating agent. LiN(i-Pr)2 could substitute the amine ligands of the two species to a different extent. THF was partially able to displace (i-Pr)2NH that solvated the species produced in toluene, but the coordination of the amine to the one produced in THF was quantitive. Correlations with given explanations are made. 相似文献
50.
Kammerer B Kahlich R Ufer M Laufer S Gleiter CH 《Rapid communications in mass spectrometry : RCM》2004,18(4):458-464
Phenprocoumon is a commonly used oral anticoagulant of the coumarin type, and has found extensive clinical use in the treatment of thrombophlebitis, pulmonary embolism and atrial fibrillation. In the course of a clinical study to investigate the influence of genetic polymorphisms of the CYP2C9 enzyme on phenprocoumon metabolism, we developed a new enantioselective liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/MS/MS) method to quantify (R)- and (S)-phenprocoumon in human plasma. HPLC separation of the enantiomers was achieved on a Chira-Grom-2 column under isocratic conditions using a water/acetonitrile/formic acid eluent. For detection and quantification a triple-quadrupole MS system was used in the selected reaction monitoring (SRM) mode. As an internal standard the structurally homologous compound warfarin was chosen. The detector response was linear with a correlation coefficient of 0.988-0.999 for (R)-phenprocoumon and 0.989-0.999 for (S)-phenprocoumon in the investigated concentration range between 62.5 and 1000 ng/mL (per enantiomer). The limit of detection (LOD) was 12.5 ng/mL. 相似文献