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101.
Daniel Canseco-González 《Journal of organometallic chemistry》2003,679(1):101-109
The complexes cis-[M(Ph2PC6H4-2-S)2] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)2(NCC6H5)2] M=Pd, Pt or NiCl2·6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] R=Ph, nBu or tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in the phosphine moiety. 相似文献
102.
人工神经网络用于锕系离子An3+水解常数pK1预测研究 总被引:1,自引:0,他引:1
0引言水解常数是金属离子水溶液化学的基础数据,对于研究水溶液中离子的状态以及进一步研究其在水溶液中的其它化学行为是必不可少的。一般金属离子(包括镧系金属离子)的水解常数数据相对较为完善,对它们水解的规律性也有不少研究,但锕系金属离子的水解常数数据迄今较缺乏,特别是重锕系的水解常数数据基本空缺犤1~5犦。这主要是因为锕系多为放射性元素,重锕系则基本是人工元素,被发现或合成较晚,即使通过核反应合成,量也往往极少(常以多少个原子个数计算),且半衰期大多很短,因而从获取样品到进行有关化学研究都相当困难。… 相似文献
103.
Thawatchai Tuntulani Praput Thavornyutikarn Sirilux Poompradub Nongnuj Jaiboon Vithaya Ruangpornvisuti Narongsak Chaichit Zouhair Asfari Jacques Vicens 《Tetrahedron》2002,58(52):10277-10285
Tripodal aza crown ether calix[4]arenes, 5a, 5b, 6a and 6b, have been synthesized. The structure of protonated 5a was elucidated by X-ray crystallography to be a self-threaded rotaxane. Complexation studies of 5a and 5b towards anions using Na+ as countercation were carried out by 1H NMR titration in dimethylsulfoxide-d6 and the mixture of chloroform-d and methanol-d4, respectively. Ligands 5a and 5b were able to form 1:1 complexes with Br−, I− and NO3− and the complexation stability varied as follows: NO3−>I−>Br−. The effect of countercation on anion complexation was also investigated. The results showed that the association constants of 5a towards Br− in the presence of various cations varied as K+>Bu4N+>Na+. The enhancement in anion complexation ability of 5a may result from the rearrangement of the tripodal ammonium unit in the presence of K+. The neutral forms, 6a and 6b, were able to form complexes with transition metal ions such as Co2+, Ni2+, Cu2+ and Zn2+. The stability of the complexes followed the sequence: Ni2+2+Cu2+Zn2+. Compounds 6a and 6b may, therefore, potentially be used as either transition metal ion or anion receptors that can be controlled by pH of the solution. 相似文献
104.
Isabel W. C. E. Arends Roger A. Sheldon Martin Wallau Ulf Schuchardt 《Angewandte Chemie (International ed. in English)》1997,36(11):1144-1163
Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O2, H2O2, and RO2H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted. 相似文献
105.
Polycrystalline Cu3P was successfully prepared under a wide variety of solvothermal conditions. The reaction of red phosphorus with several copper sources (copper metal, copper (I) iodide, copper (I) chloride and copper (II) chloride) at 150-200 °C for 1-2 days in water produced Cu3P. Products were examined with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Thermal analyses and optical spectroscopy were also performed. A detailed list of reaction conditions, products and impurity phases (where applicable) are reported. 相似文献
106.
M. J. Tiera V. A. De Oliveira H. D. Burrows M. Graça Miguel M. G. Neumann 《Colloid and polymer science》1998,276(3):206-212
The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate– methacrylic acid copolymers
with different fractions of acid groups (x) has been studied in aqueous solution at various pH values using the fluorescence of covalently bonded 9-vinyl anthracene
as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing
fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations. With Tl(I),
quenching of the anthracene group fluorescence is observed, indicating that the thallium(I) approaches the probe and suggesting
that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene
quenching data and from studies with the fluo-rescent-probe sodium pyrenetetra-sulfonate. Good agreement is obtained between
the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye–Hückel effects
and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases
in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably
as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined
from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide
as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)–carboxylate interactions contribute to the
binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it
is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in
the polymer. It is proposed that the terbium(III) interacts with six carboxylic groups on the polymer chain, with three being
coordinated and three attracted by electrostatic interactions.
Received: 10 June 1997 Accepted: 24 October 1997 相似文献
107.
海洋环境中的重金属及其对海洋生物的影响 总被引:8,自引:0,他引:8
综述了在海洋环境中重金属输入的各种途径及其重金属对海洋生物的影响,重点介绍了重金属在几种海洋生物体内的富集效应及其吸附机理,讨论了海洋重金属污染的现况,并展望了海洋重金属污染研究的前景。 相似文献
108.
BAO Ren-lie KONG Zu-ping GU Min YUE Bin WENG Lin-hong HE He-yong 《高等学校化学研究》2006,22(6):679-683
IntroductionSynthesis of natural minerals is helpful for tracingthe geological origin of mineral formation and forverifying the quality of minerals. The investigations onthe conditions for mineral formation, such as pressure,temperature, and starting mate… 相似文献
109.
Tetravalent metal phosphates (M=Zr, Ti, and Sn) were prepared and characterized by XRD, surface properties, and TG-DTA. The cation exchange and sorption behavior of these metal phosphates toward transition metal ions such as Cu(2+), Co(2+), and Ni(2+) have been studied comparatively as a function of temperature and concentration. The adsorption process was found to increases with increase in temperature and concentration. The selectivity order for alpha-titanium and alpha-tin phosphates is Cu(2+)>Co(2+)>Ni(2+), whereas for alpha-zirconium phosphate it is Cu(2+)>Ni(2+)>Co(2+). The ion exchange capacity of alpha-titanium phosphate is greater than those of other phosphates, which is explained on the basis of the surface behavior, disorderness of the system, degree of hydrolysis of incoming guest adsorbate metal ions, and structural steric hindrance of the exchangers during adsorption and sorption. The distribution coefficient, Gibbs free energy, enthalpy, and entropy values indicate that the ion-exchange processes are spontaneous. 相似文献
110.
Wang C Zhu G Li J Cai X Wei Y Zhang D Qiu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):4975-4982
We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere. 相似文献