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231.
The conditions of formation of Y, La and lanthanide (from Ce(III) to Lu) enanthates were worked out, their composition and their solubilities in water at 291 K were determined, and the conditions of their thermal decomposition were studied. They were prepared as crystalline solids with general formula Ln(C7H13O2)3·nH2O, wheren=2–10. On heating, they decompose in two or three steps. They first lose some water molecules and then decompose to the oxides directly (salts of Y and heavy lanthanides) or via the intermediate formation of Ln2O2CO3 (salts of La, Pr, Nd, Sm and Eu). Only yttrium enanthate dihydrate loses 2 water molecules on heating to form an anhydrous complex, which decomposes directly to Y2O3. The temperatures of dehydration are similar for all complexes (323–343 K), while the temperatures of oxide formation vary irregularly from 823 K for CeO2 to 1078 K for La2O3. 相似文献
232.
M. V. Alfimov S. P. Gromov O. B. Stanislavskii E. N. Ushakov O. A. Fedorova 《Russian Chemical Bulletin》1993,42(8):1385-1389
Styryl dyes containing a crown ether group and a heteroaromatic moiety with a sulfoalkylN-substituent (1a,b) undergo photocyclodimerization in acetonitrile in the presence of Mg(ClO4)2 to give only the typeA isomer of cyclobutane derivative (2a,b). The photochemical regio- and stereoselectivity of the cycloaddition is explained by self-organization of thetrans-isomers of the styryl dyes upon complexation with the Mg2+ cations into dimers with a fixed mutual arrangement of multiple bonds.For part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1449–1452, August, 1993. 相似文献
233.
A high sensitivity spectrophotometric system using a long capillary cell (LCC) detector was developed to determine dissolved inorganic phosphorus (DIP) at nanomolar concentrations in natural waters. The colorimetric chemistry used is based on the classical molybdophosphate blue technique. The radiation source is a near-infrared light-emitting diode and a silicon phototransistor is used as a detector. Method parameters were optimized for the final LCC design. With a 600-mm LCC, a detection limit (twice the standard deviation of the blank) of 1 nmol l?1 was obtained with a relative standard deviation of 6%. The working range of the instrument is 1–500 nmol l?1 DIP, and a sample volume of 10 ml is required for each analysis. The technique was applied to both fresh and marine water. The instrument is compact, relatively simple and easy to use in the laboratory and the field. 相似文献
234.
Resorc[4]arenes are compounds with interesting properties, mainly because of their ability to form host-guest complexes with the guest located inside the cavity. The size of the guest limits the complexation, as shown by a competition experiment with tetraalkylammonium ions of different size. By electroscopy ionization tandem mass spectrometric experiments on resorc[4]arene heterodimers bearing an alkali metal ion as guest, it was found that there must be two different binding mechanisms for alkali metal ions with high surface charge density (Li(+) and Na(+)) on the one hand compared with those with a lower surface charge density on the other hand (K(+), Rb(+), Cs(+)). 相似文献
235.
Shyh‐Jong Chen Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,103(2):198-214
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
236.
Tungsten(0) carbene complexes of the type (OC)5WC(NMeCH2CHCHCH2OH)R 2 (R=Me: 2a; R=Ph: 2b) were generated by aminolysis of (OC)5WC(OMe)R with cis-NHMeCH2CHCHCH2OH. Like their Cr-congeners 1, complexes 2 exist at room temperature as mixtures of Z- and E-isomers with regard to the C-N bond. The metallacyclic complexes (OC)4WC(η2-NMeCH2CHCHCH2OH)R (4) were obtained in good yields upon photo-decarbonylation of 2. Deprotonation/silylation of the complexes (OC)4MC(η2-NMeCH2CHCHCH2OH)Me (M=Cr: 3a; M=W: 4a) with one equivalent of nBuLi/Me3SiCl gave (OC)4MC(η2-NMeCH2CHCHCH2OSiMe3)CH3 (M=Cr: 5; M=W: 6), whereas with two equivalents of nBuLi/Me3SiCl complexes (OC)4MC(η2-NMeCH2CHCHCH2OSiMe3)CH2SiMe3 (M=Cr: 7; M=W: 8) were formed. Hydrolysis of the latter yielded selectively (OC)4MC(η2-NMeCH2CHCHCH2OH)CH2SiMe3 (M=Cr: 9; M=W: 10). The complexes 1-10 were analyzed in solution by one- and two-dimensional NMR spectroscopy (1H, 13C, 29Si, 1H/1H COSY, 1H/1H NOESY, 13C/1H HETCOR). 相似文献
237.
Wilfredo Hernndez Evgenia Spodine Andres Vega Rainer Richter Jan Griebel Reinhard Kirmse Uwe Schrder Lothar Beyer 《无机化学与普通化学杂志》2004,630(10):1381-1386
The N‐acyl thiourea complexes bis[N,N‐diethyl‐N′‐(p‐nitrobenzoyl)‐thioureato]copper(II) ( 1a,1b ) and bis(N,N‐diphenyl‐N′‐benzoylthioureato)copper(II) ( 2a,2b ) crystallize in each case in two modifications. X‐ray structural analysis shows that 1a and 1b are cis‐trans isomers. This is very unusual for N‐acyl thioureato complexes because with exception of one platinum(II) complex up to now only cis complexes have been found. In contrast X‐ray structural analysis of both forms 2a and 2b of the other complex shows no cis‐trans pair. Both modifications are cis complexes. In solution both isomers of the copper(II) complexes are observable by EPR spectroscopy. 相似文献
238.
This paper proposes a quick, novel method for tin determination in organotin chemicals by slurry nebulization inductively coupled plasma atomic emission (ICP-AES) spectrometry. The method was tested by the measurement of five organotin carboxylate complexes of known composition for obtaining simple stoichiometric data. The slurries were prepared by first dissolving the organotins in an adequate solvent (methanol, pyridine or acetone) well miscible with water and then adding this solution drop-by-drop to a 0.005% TX-100 tenzide solution while maintaining intensive mixing. Dynamic laser light scattering experiments showed that the average equivalent particle size in the resulting slurry was ≈0.3 μm for all samples and solvents. Under suitable ICP-AES measuring conditions, the signal recoveries were found to be between 101.8 and 106.6%, which allowed direct nebulization and calibration against aqueous solutions. Typically, 70 μg l−1 detection limit and 1–5% relative S.D. on five replicates can be achieved by the described method. 相似文献
239.
环糊精及其包结物的电化学研究及应用 总被引:2,自引:1,他引:2
本文概述了近年来环糊精及其包结物的电化学研究及应用,同时介绍了我们实验室开展的关于环糊精电化学研究的一些工作。 相似文献
240.
The interaction of carbenium ion pairs with silica is studied by means of UV-spectroscopy, electrokinetic and adsorption measurements using triphenylmethyl derivatives, (RC6H4)3CX, (X=F, Cl, Br, SCN, OH; R=Cl, I, H, CH3, C(CH3)3, OCH3, N(CH3)2) in interaction with silica particles suspended in 1,2-dichloroethane. The adsorption of triarylmethyl-halides onto silica is accompanied by the heterolytic dissociation of the tertiary carbonhalogen bond. The degree of ionization depends on the basicity of the counter anion and acidity of the cation, respectively. The influences of both concentration and structure of triarylmethyl halides on the zeta-potential are discussed with regard to steric and electronic factor. The zeta-potential values of the adsorbates decrease significantly, as compared with the free silica surface, from a certain triarylmethyl halide concentration where ionization takes place, to a constant level which is characteristic of the carbenium ion pair. These constant zeta-potential values of the adsorbates depend on the basicity of the counter ion and the
p
Hammett constants of the ring substitutents, with exclusion of sterically hindered substituents and salt derivatives, e.g., crystal violet and malachite green. 相似文献