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11.
Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na2MnF5 and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with
eff
and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.
8. Mitt.: Mh. Chem.106, 483 (1975). 相似文献
8. Mitt.: Mh. Chem.106, 483 (1975). 相似文献
12.
R.R. Adžić D.N. Simić A.R. Despić D.M. Dražić 《Journal of Electroanalytical Chemistry》1975,65(2):587-601
It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen. 相似文献
13.
14.
In the framework of path integrals we present a solution to the Schrödinger equation for a free particle confined to the half-linex > 0. A solution in question corresponds to the boundary condition (/x) (0,t)= (0,t) where is a real constant. 相似文献
15.
M. Rotter B. Sedlák J. Englich P. Čížek M. Finger P. Malinský 《Czechoslovak Journal of Physics》1986,36(11):1331-1335
The results of NMR/ON measurements on56,57,60Co isotopes in iron are presented in the paper. To avoid the uncertainties caused by local demagnetizing field inhomogeneities the measurements on two cobalt isotopes in one sample have been carried out. The values of nuclear-factors ratios
57/
60=1·805(20),
60/
56 = 0·761(20),
56/
57 = 0·726(20) and hyperfme anomalies56
60 = –0·036(10),60
57 = 0·017(10) and57
56 = 0·018(10) have been calculated from the experimental results.Dedicated to the 30th anniversary of the Joint Institute for Nuclear Research. 相似文献
16.
Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (4
C
1) and equatorial (1
C
4) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22. 相似文献
17.
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
18.
Yellow-orange single crystals of CuSbF6, were prepared by reacting Cu wire (∼10 mmol) with SbF5 (∼3 mmol) in liquid anhydrous hydrogen fluoride (aHF) and by reduction of Cu(SbF6)2 with Cu metal in aHF. CuSbF6 crystallizes rhombohedral at 296 K with the LiSbF6 structure type, with a = 530.4(4) pm, c = 1453(1) pm and Z = 3, space group R (no. 148). The structure is dominated by isolated layers of regular [SbF6]− octahedra and Cu+ cations.An attempt to prepare CuF by reaction between CuSbF6 and CsF in aHF at ∼190 K failed. Instead of CuF, a mixture of Cu and CuF2 was obtained. 相似文献
19.
Zusammenfassung Die Reaktion von 1-Nitroso-2-naphthol mit 1-und 2-Naphthol sowie die Reaktion von 2-Nitroso-1-naphthol mit 2-Naphthol in Äthanol und in Äther bei Anwesenheit von HNO3 gibt 5H-Dibenzo[a,j]phenoxazon-(5) (I), 5H-Dibenzo[a,j]phenoxazon-(5)-14-oxid (II), 5H-Dibenzo[a,h]phenoxazon-(5) (III) sowie 5H-Dibenzo[a,h]phenoxazon-(5)-14-oxid (IV). Es wurde ein Reaktionsmechanismus vorgeschlagen und die Konstitution der hergestellten Verbindungen spektrophotometrisch und potentiometrisch bestimmt.
Mit 4 Abbildungen 相似文献
The reaction of 1-nitroso-2-naphthol with 2-and 2-naphthol and the reaction of 2-nitroso-1-naphthol with 2-naphthol in ethanol or ether in the presence of nitric acid have been studied. The main reaction products isolated were the dibenzophenoxazones I–IV. The reaction mechanism for their formation is proposed.
Mit 4 Abbildungen 相似文献
20.
The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent
mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol
solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant
in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching
the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the
presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity,
and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering
that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.
Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical
Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10
June 2005. 相似文献