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41.
M. Kabešová I. Vargová T. Šramko J. Gažo 《Journal of Thermal Analysis and Calorimetry》1978,13(1):65-70
The influence of the position of the CH3 group in picoline and lutidine ligands on the degree of chemical change of the NCS groups in coordination compounds of the type Cu(NCS)2L2 (whereL=2-, 3- and 4-picoline, and 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine) is dealt with. The most marked effect of the CH3 group is found to be exerted in position 4. This effect of the methyl group on the degree of chemical change points to the mutual influence of the ligands in coordination compounds of Cu(II).
Zusammenfassung Der Artikel befaßt sich mit dem Einfluß der Lage der CH3 Gruppe in Pikolinen und Lutidinen als Liganden auf den Grad der chemischen Änderungen der Gruppen NSC in Koordinationsverbindungen des Typs Cu(NCS)2L2 (L=2-, 3- und 4-Pikoline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- und 3,5-Lutidine). Der ausgeprägteste Effekt der CH3 Gruppe wurde in der Position 4 beobachtet. Dieser Einfluß der Methylgruppe auf das Ausmaß der chemischen Änderungen deutet auch auf die gegenseitige Wirkung der Liganden in Koordinationsverbindungen von Cu(II).
Résumé L'article a trait à l'influence de la position du groupe CH2 dans les picolines et lutidines, en tant que ligands, sur le degré des changements chimiques des groupes SCN dans les composés de coordination du type Cu(SCN)2L2 (L=2-, 3 et 4-picoline, 2,3-, 2,4-,2,5-, 2,6-, 3,4- et 3,6-lutidine). L'effet le plus prononcé du groupe CH3 s'observe en position 4. Cette influence du groupe méthyle sur le degré des changements chimiques indique aussi l'influence mutuelle des ligands dans les composés de coordination du Cu(II).
- , , NCS Cu(NCS)2,L2, L=2-, 3- 4- , 2.3-, 2.4-, 2.5-, 2.6-, 3.4- 3.5-. , 4. Cu(II).相似文献
42.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
43.
Berezkin Victor G. Mardanov Robert G. Moiseew Aleksey A. Malinowska Irena Różyło Jan K. 《平面色谱法杂志一现代薄层色谱法》2002,15(5):377-379
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
44.
Aguado GP Moglioni AG García-Expósito E Branchadell V Ortuño RM 《The Journal of organic chemistry》2004,69(23):7971-7978
The hydrogenation reactions of several cyclobutyl enamides derived from (-)-alpha-pinene or (-)-verbenone have been investigated by using different catalysts. The chiralities of both the substrate and the catalyst as well as the Z/E stereochemistry of the double bond have been considered, and the observed diastereoselectivity has been rationalized. For enamides with the double bond separated from the cyclobutane by a methylene, the Wilkinson catalyst did not induce any diastereoselection, but excellent diastereoselectivity was observed when using Et-DuPHOS-Rh and ChiraPHOS-Rh. The configuration of the new stereogenic center was catalyst-dependent and can be rationalized according to the Halpern mechanism. For (Z)-enamides with the double bond directly linked to the cyclobutane ring, the chirality of the substrate governed the diastereoselection and the Halpern mechanism seemed not to be operative in the hydrogenation with ChiraPHOS, with the configuration of the new stereogenic center being determined by steric effects. On the contrary, the chirality of the catalyst was the factor determining the stereochemistry of the major products with alkyl-DuPHOS-Rh. Z/E stereochemistry influenced the stereodifferentiation, and a different behavior for each Z or E stereoisomer was found. For both (Z)- and (E)-enamides, some instances of match/mismatch between the chirality of the substrate and that of the catalyst were observed. As a result of all of these studies, a series of new cyclobutyl alpha-amino acids has been synthesized. These products are interesting to incorporate into conformationally constrained peptides. 相似文献
45.
H. A. Ergül S. Topcuo?lu E. Ölmez Ç. K?rbaşo?lu 《Journal of Radioanalytical and Nuclear Chemistry》2006,268(1):133-136
Summary Radionuclide (137Cs, 238U, 232Th and 40K) concentrations were determined in a sediment trap and bottom sediment samples collected from a station at the eastern Turkish
coast of the Black Sea. The specific activity of the 137Cs radionuclide in the settling particles ranged from 0.04±0.01 to 0.10±0.02 Bq. g-1dry weight. The calculated flux rate of the 137Cs was between 0.37 and 2.59 Bq. m-2. d-1in the sampling periods of 2002 and 2003. The 137Cs concentration in the bottom sediment profile were between 0.039±0.013-9.083±0.017 Bq. g-1dry weight in the same station. The vertical profile of the radionuclides suggests that they have little mobility during the
17 years after the Chernobyl accident. 相似文献
46.
The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10−4 mol L−1; ammonium chloride buffer: 0.10 mol L−1 (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10−9 mol L−1 for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays. 相似文献
47.
48.
Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT)
species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase
extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column
derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C18 enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors
up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole
process have been determined. The method has been applied to the determination of organotin species in spiked natural water
samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low
ng L−1 level (1–3 ng Sn L−1 for DPhT, DBT, and PhT and 40 ng Sn L−1 for TBT when 250 mL spiked sea water is processed.) 相似文献
49.
The main features of transition structures associated with eight-electron electrocyclic reactions have been studied with Density Functional Theory. It is found that conrotatory electrocyclization reaction of (3Z,5Z)-octa-1,3,5,7-tetraenes takes place via M?bius aromatic transition structures of helical conformation. The reaction is completely periselective. In general, transition structures having outward substituents are preferred with respect to the inward transition structures, irrespective of the pi-donor or pi-acceptor character of the substituent. In contrast with four-electron thermal conrotatory electrocyclic reactions, there is no satisfactory correlation between the difference in energy of activation between inward and outward substituents and the Taft resonance sigma(R) parameter. 相似文献
50.
AurelioG. Cskÿ Rocío Medel M.Carmen Murcia Joaquín Plumet 《Helvetica chimica acta》2005,88(6):1387-1396
A new method for the synthesis of spiro‐β‐lactams tethered to tetrahydrofuran rings is described. The procedure is based on Ru‐catalyzed metathesis sequences with oxanorbornene precursors easily obtained by the Staudinger [2+2] cycloaddition of related imines. 相似文献