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21.
Konrad Kowalski Janusz Zakrzewski S?awomir Domaga?a 《Journal of organometallic chemistry》2006,691(18):3902-3908
The synthesis of 1′-ethynyl-2,5-dimethylazaferrocene is reported along with its cyclic voltammetry measurements and the X-ray structure determination of its W(CO)5-complex. Basic coordination and organic chemistry of 1′-ethynyl-2,5-dimethylazaferrocene is also presented via derivatives incorporating cis-Pt(dppe) and Si(Et)3 units. 相似文献
22.
Tritium exchange at C-8 of xanthosine, theobromine, 1-, 3- and 7-methylxanthine in water has been studied. The rates of detritiation of these compounds have been determined over a pH range at constant temperature. Several mechanisms of exchange involving various ionic forms of substrate operating at different pH have been suggested. 相似文献
23.
Jerzy Lange Elzbieta Pytlewska Jan Plenkiewicz Tomasz Kulinski Janina Karolak-Wojciechowska Slawomir Rump 《Journal of heterocyclic chemistry》1997,34(2):389-396
Ethoxycarbonylalkylidene derivatives 2 and 6 of the title hydrazones were obtained in the reaction with ethyl pyruvate or ethyl aroylformate and ethyl acetoacetate, respectively, in methanol. Both compounds were mixtures of geometric isomers with high predominance of one of them. Nmr spectroscopy revealed an unexpected magnetic non-equivalence of the CH2 protons in the ester ethyl group of the major isomer of 6 . On heating (?200°) in an inert medium or on refluxing in ethanolic sodium ethoxide 2 cyclized to the corresponding pyridazino[6,1-c]-triazines 4 , whereas 6 formed pyrazolylpyridazines 7 . The structure of the latter was unambigously established by X-ray analysis. Alkylation of 4a with benzyl bromide in the presence of tetrabutylammonium bromide occurred selectively on the pyridazine N atom. 相似文献
24.
Rode MF Roszak S Szymczak JJ Sadlej J Leszczynski J 《The Journal of chemical physics》2004,121(13):6277-6281
The results of the theoretical study of ground state potential energy surfaces for the chlorine-acetonitrile anion and its photodetachment product are presented. The shallow potential surfaces allow for the nondefinitive position of the chlorine within the complex. The dissociation energy of the neutral complex, estimated through the thermodynamic cycle, indicates significant structural changes due to the photodetachment process. The excess negative charge is localized mostly on the chlorine atom, and the electron detachment proceeds as an electron is removed from chlorine. The process leads to drastic changes in the electrostatic interactions within the complex. The first electronic excited state corresponds to the excess electron transfer from chlorine to acetonitrile fragment. This state is a precursor of the observed charge-transfer-to-solvent state. 相似文献
25.
M. Zakrzewski D. D. Klug J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(3):237-247
A high-pressure phase of the clathrate hydrate of tetrahydrofuran was prepared by freezing a liquid phase of overall composition THF · 7 H2O under a pressure of 3.0 kbar, or by pressurizing the solid structure II THF hydrate of 255K to 3.4 kbar. Unfortunately, the products recovered at 77K were always mixed phase materials as shown by X-ray powder diffraction. A number of diffraction lines could be indexed in terms of the cubic structure I hydrate with a slightly expanded lattice parameter, 12.08 Å, giving some support to Dyadin's idea that the high pressure phase transition involves a conversion of Structure II to Structure I. Other phases observed in the recovered product include Ice IX and amorphous materials. The reversion of the high pressure sample to the structure II hydrate was followed by differential scanning calorimetry. At ambient pressure, the high pressure sample converts slowly back to Structure II hydrate event at 77K.NRCC No. 35786. 相似文献
26.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
27.
We present an analytical expression of the Wigner distribution function (WDF) for the bound eigenstates of the rotating Morse oscillator (RMO). The effect of rotational excitation on the WDF on the quantum phase space has been demonstrated. This effect has been visualized by a series of contour diagrams for given rovibrational quantum states. Rotations of the molecule have been proved to qualitatively and quantitatively change the Wigner function. As a result, the most probable distance between atoms in a rotating molecule changes, and depends on the parity of the vibrational quantum number. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
28.
We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH4)2SiF6 treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm−1 (AlO)(SiO)2SiO1HAl(OSi)3 and more acidic 3625 cm−1 (SiO)3SiO1HAl(OSi)3 groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in 29Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm−1 hydroxyls interacting with extraframework Al species. 相似文献
29.
Micha Kijak Anna Zieli ska Charles Chamchoumis Jerzy Herbich Randolph P. Thummel Jacek Waluk 《Chemical physics letters》2004,400(4-6):279-285
Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role. 相似文献
30.
The lithium and europium(III) cryptates of a macrobicyclic ligand 1 incorporating the 3,3′-biisoquinoline 2,2′-dioxide 2 have been prepared. The Eu(III) complex [Eu(2)2]Cl3 has also been obtained. These Eu(III) complexes present characteristic 1H-NMR spectra containing markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been determined. 相似文献