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261.
Usein M Dzhemilev Vladimir A D'yakonov Leila O Khafizova Askhat G Ibragimov 《Tetrahedron》2004,60(6):1287-1291
Cyclo- and carbomagnesiation of 1,2-dienes with EtMgR′ (R′=Et, Br) in the presence of Cp2ZrCl2 catalyst lead to alkylidenemagnesiocyclopentanes. Deuterolysis provides insights into the reaction pathways. 相似文献
262.
Physicochemical and catalytic properties of phosphorus and boron modified HZSM-5 zeolites treated with 100% steam at 673K were investigated.The acidity and distribution of acidic sites were studied by infrared spectroscopy using pyridine as probe molecule and temperature programmed desortion (TPD) of ammonia.The structure of the samples was characterized by XRD,and the textural properties of the catalysts were determined by nitrogen isothermal adsorption-desorption measurements and scanning electron microscopy(SEM).The XRD results show that the modified samples have no novel crystalline phase,indicating a high dispersion of phosphorus and boron species.After treatment,the microporous volume and surface area of the samples markedly decrease,implying the bolockage of the channel.The nitrogen adsorption-desorption measurements suggest that the isothermal type of all samples is a combination of isothermal type Ⅰ and Ⅳ,and all hysteresis loops resemble the H4-type in the IUPAC classification.The total acidity of the modified samples,determined by pyrldine adsorption IR and TPD of ammonia,decreases in contrast to that of the parent HZSM-5.The conversion of n-heptane over P and B steammodified HZSM-5 is higher than that of P and B-modified HZSM-5 zeolites but lower than that of the parent HZSM-5. 相似文献
263.
Kh. B. Kushkhov M. K. Vindizheva R. A. Karashaeva 《Russian Journal of Electrochemistry》2006,42(8):830-835
The mechanism of electroreduction of cerium ions in equimolar KCl-NaCl melt is explored at 973 K. The effect of the anionic composition of the melt on the electroreduction of cerium ions is studied. It is shown that the electrodeposition of metal cerium from halide melts on a silver electrode is the primary electrochemical process that occurs at potentials more positive than those corresponding to the supporting-electrolyte decomposition. The electroreduction of chloride complexes of cerium on a silver electrode in the melt in both steady-and non-steady-state polarization modes at rates below V ≤ 0.5 V/s is limited by the diffusion delivery; at higher polarization rates, the charge-transfer stage predominates. 相似文献
264.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
265.
266.
Complexes have been prepared by treatment ofn-decylammonium beidellite with mixtures ofn-decanol andn-tetradecanol with different concentrations. Measurements of the basal spacings of the obtained complexes have been performed in a wide range of temperatures. Three different bilayer phases have been established between (20 and 70°C: the
i(C10) phases (=bilayers ofn-decyl chains); the
i(C10/C14) phases (=mixed bilayers ofn-decyl andn-tetradecyl chains in molar ratio approximately 1:1) and the
i(C14) phases (=bilayer ofn-tetradecy 1 chains with then-decylammonium ions included). In all bilayer phases the chains stand perpendicular to the silicate interfaces. In definite concentration ranges two of the phases coexist, i.e., miscibility gaps occur, which disappear at temperatures higher than the temperature of the
i/ transition. The miscibility gaps are reversible with temperature. The composition of the intercalated bilayers has been studied by HPLC of the excess alkanol mixture separated from the beidellite complexes after the equilibrium has been reached. There is preferential adsorption of one of two alkanols from the mixture, which is in agreement with the observed miscibility gaps. The space filling problem as well as the structure of the three bilayer phases observed have been discussed. 相似文献
267.
Dagobert Achatz Markus A. Lang Alfons Vlkl Wolf Peter Fehlhammer Wolfgang Beck 《无机化学与普通化学杂志》2005,631(12):2339-2346
Carbonyl Complexes of Chromium, Molybdenum and Tungsten with Isocyano Acetate. Reactions of Coordinated Isocyanoacetate. Stabilization of Isocyanoacetic Acid and Isocyanoacetyl Chloride at the Metal Atom. Isocyanopeptides The reactions of [(OC)5MCNCH2CO2Et] (M = Cr, W) with Na[N(SiMe3)2] or with KOH afford the isocyanoacetate complexes [(OC)5MCNCH2CO2]? ( 1,2 ). Similarly, the complex [(OC)3Mo(CNCH2CO2?Li+)3] ( 4 ) was obtained from [(OC)3Mo(CNCH2CO2Et)3] ( 3 ) and LiOH. Protonation of 1 and 2 affords the sublimable isocyanoacetic acid complexes [(OC)5MCNCH2CO2H] ( 5 , 6 ; M = Cr, W) in which the functional isocyanide is stabilized at the metal atom. Reactions of [(OC)5WCNCH2CO2?K+] and of [(OC)3Mo(CNCH2CO2?Li+)3] with oxalyl dichloride give the isocyanoacetyl chloride compounds [(OC)5WCNCH2COCl] ( 9 ) (sublimable) and [(OC)3Mo(CNCH2COCl)3] ( 10 ); the latter ( 10 ) was not isolated. Complexes 9 and 10 were reacted in situ with β‐alanine, glycine, phenylalanine and methionine esters as well as the peptide esters GlyGlyOEt, PhePheOMe, Phe‐β‐AlaOMe, and GlyGlyGlyOMe to form the isocyanoacetyl amino acid esters ( 11 ‐ 14 ) and the isocyanoacetyl peptide esters ( 15 ‐ 18 ) which are stabilized at the molybdenum atom. 相似文献
268.
Sven Rau 《Journal of organometallic chemistry》2004,689(22):3582-3592
The binuclear complex [(acac)Pd(oxam)Pd(acac)] 1 (oxam: tetraphenyl oxalic amidinate) has been prepared from H2oxam and Pd(acac)2 in excellent yield. The complex was characterized by elemental analyses, mass spectroscopy, 1H NMR, 13C NMR spectroscopy and in the solid state by X-ray single crystal diffraction analyses. 1 consists of a bimetallic centrosymmetric unit in which the planar oxam ligand acts in a bis-chelating fashion. Each palladium center is in a planar environment.The complex 1 acts as highly selective pre-catalyst in the copper-free Sonogashira reaction between 4-bromoacetophenone and phenylacetylene. Its long-time catalytic activity is higher than that of the related binuclear complex 2 (oxam: tetra-p-tolyl oxalic amidinate) or that of the trinuclear compound [(acac)Pd(oxam)Zn(oxam)Pd(acac)] (3), the solid-state structure of which was also determined by an X-ray structural analysis of single crystals. In addition, 2 is an active and extremely selective pre-catalyst for the Negishi reaction between 3,5,6,8-tetrabromophenanthroline and R-CC-ZnCl (R: Ph, (iprop)3Si) to form tetra-alkyne-substituted derivatives. 相似文献
269.
A. P. Borisov L. A. Petrova T. P. Karpova V. D. Makhaev 《Russian Chemical Bulletin》1994,43(12):2107-2109
Tris(4-imino-2-pentanonato)chromium was prepared by solid-state synthesis under conditions of mechanical activation of a mixture of chromium(III) chloride and sodium 4-imino-2-pentanonate and characterized by IR spectroscopy, X-ray diffraction, and electronic absorption spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2227–2229, December, 1994.The present work was carried out as a part of Project No. 1.164 Mechanochemical Synthesis of Complex Compounds of The State Scientific and Technical Program Ecologically Safe Processes in Chemistry and Chemical Technology with the financial support of the Ministry of Science of the RF. 相似文献
270.
Donia A. M. El-Boraey H. A. El-Samalehy M. F. 《Journal of Thermal Analysis and Calorimetry》2003,73(3):987-1000
Manganese and iron complexes of Schiff bases derived from 6-formylkhellin were prepared and characterized. Complexes of o-phenylenediamine derivative (ligand (I)) are monomeric or dimeric whereas those of p-phenylenediamine derivative (ligand (II)) are polymeric. The complexes obtained are characterized by a lower magnetic moment
values. The complexes also have different solvent of crystallization with different nature of interaction. The thermal behaviour
of the ligands and their metal complexes was investigated by means of DTA, TG, IR and X-ray diffraction spectroscopy. Ligand
(I) shows different thermal behaviour from that of ligands (II) and (III). The complexes of ligand (II) give abnormal oxides
as a final product during their thermal decomposition.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献