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41.
Studies of the vibrational spectra of matrix-isolated M+NO
3
–
ion pairs have been extended to glassy aprotic solvents. The deuterated form of the solvents DMSO, THF, and ACN have windows through the 7- nitrate ionv
3(e) mode infrared region, so it was possible to clearly observe the splitting of the degeneracy of this mode,v
3, produced by the contacting, but solvated, alkali metal cation. Primary attention has been directed to the extent to which this splitting is reduced relative to the argon matrix values. This reduction, which reflects electron-density transfer from the solvating molecules to the ion pairs, is comparable to that observed for H2O and NH3 matrices as the splitting is reduced to 20–35% of the argon-matrix values. The extent of reduction ofv
3 for the different solvents has been related to Gutmann's donicity number scale with the correlation holding well for solvent molecules of comparable size, DMSO, THF and DMF, but breaking down for the smaller linear ACN, apparently because of more molecules in the cation solvation sphere. The matrix data have also been used, through comparison with spectra for saturated liquid solutions of Li+NO
3
–
, to show that the contact ion pair is the dominant species in liquid THF and ACN, whereas the ions are largely solvent separated in DMSO. 相似文献
42.
B. L. Tumanskii V. V. Bashilov N. N. Bubnov S. P. Solodovnikov V. I. Sokolov 《Russian Chemical Bulletin》1994,43(5):884-886
Using ESR spectroscopy, the reaction of P(O)(OPri)2 phosphoryl radicals with C60ML2 (M=Pd, Pt) was studied and the spin-adducts formed were shown to be unstable under the reaction conditions. The 5-addition of Pt(PPh3)4 to the dimer of phosphorylfullerenyl radicals results in metal-containing dimers (RO)2(O)PL2MC60-C60ML2P(O)(OR)2, which dissociate when exposed to visible light to afford C60ML2P(O)(OR)2 radicals; ML2 in these complexes is located in different positions in relation to the radical center. As a result, the ESR spectra contain the superposition of at least five signals of radicals that differ in HFS constants andg-factors.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 938–940, May, 1994.The present work was supported by the Russian Foundation for Basic Research (Projects 93-03-18725 and 93-03-4101). 相似文献
43.
The gas-phase electronic absorption spectra of (6-C6R6)2Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3dz2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO. 相似文献
44.
Unicyclic Graphs with Minimal Energy 总被引:7,自引:0,他引:7
Yaoping Hou 《Journal of mathematical chemistry》2001,29(3):163-168
If G is a graph and 1,2,...,
n
are its eigenvalues, then the energy of G is defined as E(G)=|1|+|2|++|
n
|. Let S
n
3 be the graph obtained from the star graph with n vertices by adding an edge. In this paper we prove that S
n
3 is the unique minimal energy graph among all unicyclic graphs with n vertices (n6). 相似文献
45.
Three new serratanes were isolated from the nonsaponifiable fraction of western white pine ( Dougl.) bark. The compounds were shown to be 3β-methoxyserrat-14-ene-21α,30-diol (), 3β-methoxyserrat-14-ene-21α, 29-diol (), and 3β-methoxyserrat-14-ene-21β,30-diol (), by a combination of chemical, and spectral methods. 相似文献
46.
Yu. V. Tomilov I. V. Kostyuchenko G. P. Okonnishnikova I. P. Klimenko E. V. Shulishov 《Russian Chemical Bulletin》2006,55(11):2008-2012
A new way of generating cyclopropyl radicals in the base-catalyzed decomposition of N-cyclopropyl-N-nitrosourea in the presence of organic reducing agents (1-phenylpyrazolidin-3-one and 4-methoxyphenol) was developed. The
cyclopropyl radical generated under these conditions can not only abstract a proton from the substrate to give cyclopropane
but also form C-C or C-Br bonds in reactions with aromatic substrates or polybromomethanes.
Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1934–1938, November, 2006. 相似文献
47.
Krystyna Holderna-Natkaniec Ireneusz Natkaniec Weronika Kasperkowiak Elzbieta Sciesinska Jacek Sciesinski Edward Mikuli 《Journal of Molecular Structure》2006,790(1-3):94-113
FTIR and IINS spectra of 6-Furfurylaminopurine (6-FAP) and 6-Benzylaminopurine (6-BAP) taken at different temperatures have been analysed and compared with the spectra calculated by the ab initio DFT/B3LYP method and the semiempirical PM3 method in the isolated molecule approximation, for the tautomers N3-H, N7-H and N9-H, and dimers with hydrogen bonds. For 6-FAP the best agreement between the calculated and experimental (at 20 K) spectra has been found for the N9-H tautomer, whose structure was established by X-ray diffraction. For 6-BAP the analogous agreement for the N9-H tautomer structure has been poor and much better for the N7-H tautomer. The vibrational spectra calculated for dimers of the molecules studied involved in hydrogen bonds, permitted also an interpretation of the bands whose positions and FWHM in the FTIR spectra changed with temperature. 相似文献
48.
49.
Kovácik V Bekesová S Tvaroska I Hirsch J Chmelík J 《Journal of mass spectrometry : JMS》2004,39(12):1554-1561
Fragmentation mechanisms of electrospray ionization (ESI) mass spectrometry of aldobiuronic and pseudoaldobiuronic acid derivatives were elucidated by multistage mass spectrometric (MS(n), n = 2-5) measurements of selected ions. Characteristic under the conditions of ESI-MS analysis is the production of alkali metal (Na and K) cationized adducts. The probability the of locations of Na cations in per-O-methylated compounds was proved by quantum chemical calculations, using the Jaguar program. The most probably position of alkali metal attachment is the carboxy group of the methoxycarbonyl C-5 group of the uronic acid unit. Characteristic cleavages vary according the kind of O-derivatization. In most cases they take place on the acidic part of the dimer and at the interglycosidic oxygen atom. As a result, the criteria for the differentiation of aldobiouronic and pseudoaldobiouronic acids derivatives were elucidated. 相似文献
50.
In this article, the results of calculations of scattering spectra of low-absorptive spherical particles are presented. It was obtained using different approximate and numerical methods. The comparative evaluations of application of single scattering approximation, the average field approximation and of the methods of computer modeling on the basis of Monte-Carlo method on various scattering multiplicity were performed. The comparison demonstrates the good agreement of calculated results with experimental scattering spectra of eye lens. By using the obtained spectral data the colour coordinates are calculated. The regularities of changes in colour characteristics in dependence of disperse system parameters are analyzed. 相似文献