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探究了水溶液中Fe3+与S2-的反应,得出几点结论:生成Fe2S3的沉淀反应是动力学优势反应,生成Fe2+和S的氧化还原反应是热力学优势反应;发现Fe2S3可以与Fe3+反应生成S和Fe2+,Fe2S3在酸性条件下不稳定;在弱碱性条件下,Fe3+也有与HS-发生氧化还原反应的倾向;Fe3+在水溶液中主要以水解产物[Fe(H2O)6-n(OH)n](3-n)+(n=1,2)存在,[Fe(H2O)6-n(OH)n](3-n)+的氧化性很弱,难以将H2S或HS-氧化,却易与S2-结合生成Ksp极小的Fe2S3沉淀。 相似文献
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近年来 ,金属羰基化合物与异硫氰酸苯酯 Ph NCS反应曾有过报道 [1 -3 ] ,但反应条件各异 ,多半得到一取代产物。本文用 Fe3 (CO) 1 2 与 Ph NCS在温和条件下缓慢反应 ,除了得到一取代产物外 ,还得到一个新的二取代产物。通过元素分析、IR、MS、1 H NMR、1 3 C NMR和 X- ray四园衍射表征 ,确定它们的化学式为 Fe3 (CO) 8(CNPh) (μ3 - S) 2 ( )和 Fe3 (CO) 7(CNPh) 2 (μ3 - S) 2( )。实 验 部 分合成采用 Schlenk技术在氮气保护下进行 ,所使用溶剂经过脱气脱水处理。一 .簇合物的合成0 .5 g(1.0 mmol) Fe3 (CO) 1 2 和 … 相似文献
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羰基铁-硫醇-三乙胺反应体系的研究, μ-酰基与μ-烯基铁硫配合物的合成系脱羰反应动力学 总被引:1,自引:0,他引:1
本文由反式巴豆酰氯与活性中间物[(μ-CO)(μ-R1S)Fe2(CO)6]ˉEt3N^+反应, 合成了两个新的μ-酰基铁硫配合物(μ-R1S)(μ-CH5CH=CHCO)Fe2(CO)6(R1=Et, Bu^t)和三个新的μ-烯基铁硫配合物(μ-R1S)(μ-CH3CH=CH)Fe2(CO)6(R1=Et, Bu^+, CH2=CHCH2), 此外还研究了μ-酰基配合物脱羰生成μ-烯基配合物的反应动力学, 证明为一级反应, 并求得在一定条件下的速率常数和半衰期。 相似文献
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本文由反式巴豆酰氯与活性中间物[(μ-CO)(μ-R1S)Fe2(CO)6]ˉEt3N^+反应, 合成了两个新的μ-酰基铁硫配合物(μ-R1S)(μ-CH5CH=CHCO)Fe2(CO)6(R1=Et, Bu^t)和三个新的μ-烯基铁硫配合物(μ-R1S)(μ-CH3CH=CH)Fe2(CO)6(R1=Et, Bu^+, CH2=CHCH2), 此外还研究了μ-酰基配合物脱羰生成μ-烯基配合物的反应动力学, 证明为一级反应, 并求得在一定条件下的速率常数和半衰期。 相似文献
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具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。 相似文献
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具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。 相似文献
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Cp^*Cr(NO)(CO)~2与Fe(C~5H~4S)~2S反应,形成氧化-还原产物Cp^*Cr(NO)(SC~5H~4)~2Fe(1)。双杂核二茂铁化合物Cp^*M(NO)(EC~5H~4)~2Fe[M=Mo,E=S(2a),Se(2b);M=W,E=S(4a),Se(4b)]、CpMo(NO)(SC~5H~4)~2Fe(3)、Cp~2Mo(SeC~5H~4)~2Fe(6)和Cp~2W(SC~5H~4)~2Fe(7)可通过Fe(C~5H~4ELi)~2.2THF(E=S,Se)与Cp^*M(NO)I~2(M=Mo,W)、[CpMo(MO)I~2]~2或Cp~2MCl~2(M=Mo,W)反应制得。三核杂原子二茂铁化合物[Cp^*Cr(NO)~2]~2(EC~5H~4)~2Fe[E=S(8a),Se(8b)],由Fe(C~5H~4ELi)~2.2THF(E=S,Se)与二倍摩尔量的Cp^*Cr(NO)~2I反应制备。通过AgBF~4氧化2a得到二茂铁离子型化合物[Cp^*Mo(NO)(SC~5H~4)~2Fe]^+BF~4^-(5)。采用元素分析、红外光谱、^1H和^1^3CNMR谱以及EI-MS表征了所合成的新型化合物。 相似文献
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Panyushkin V. T. Sukhno I. V. Vodopetova N. L. 《Russian Journal of General Chemistry》2003,73(4):507-510
The dependence of the NMR chemical shift in the system containing complexes of a paramagnetic cation PL and PL2 on the concentration of a diamagnetic salt was simulated. The complexation in the system paramagnetic ion (Tm3
+)-diamagnetic ion (Mg2
+)-carboxylic acid (acetic, propionic, n-butyric) was studied experimentally. The effect of the second cation on the calculated complexation constants was detected. 相似文献
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Marian Olaru Alexandra Mischin Lorraine A. Malaspina Stefan Mebs Jens Beckmann 《Angewandte Chemie (International ed. in English)》2020,59(4):1581-1584
The bis(ferrocenyl)phosphenium ion, [Fc2P]+, reported by Cowley et al. (J. Am. Chem. Soc. 1981 , 103, 714–715), was the only claimed donor‐free divalent phosphenium ion. Our examination of the molecular and electronic structure reveals that [Fc2P]+ possesses significant intramolecular Fe???P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc2P]+ undergoes complex formation with the Lewis bases PPh3 and IPr to give the donor–acceptor complexes [Fc2P(PPh3)]+ and [Fc2P(IPr)]+ (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazole‐2‐ylidene). 相似文献
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Ion recognition properties of self-assembled monolayers (SAMs) 总被引:1,自引:0,他引:1
In the search for new sensors, self-assembled monolayers (SAMs) have gained intensive interest due to their nanometre size, highly-ordered structures, and molecular recognition properties. This article presents an overview of ion recognition at SAM-modified surface/solution interfaces, and brings up to date the most notable examples for the sensing of cations and anions. Sensing is achieved with SAMs containing redox active and inactive receptors using techniques such as fluorescence spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. 相似文献
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Martins AM Ascenso JR Costa SM Dias AR Ferreira H Ferreira JA 《Inorganic chemistry》2005,44(24):9017-9022
[Ti[N(Ph)SiMe2]3-tacn]X complexes (X = Cl, 1; I, 2; PF6, 3; BPh4, 4) were studied by NMR and electron absorption and emission methods, which showed that these compounds exist in bromobenzene and dichloromethane solutions as ion pairs. The significant modifications observed in the proton resonances of tacn in C6D5Br, which follow the sequence BPh(4-) > or = PF(6-) > or = I- approximately Cl-, are a qualitative indication of the strength of the interactions that depend on the anion. The reaction of 2 with LiNMe2 led to [Ti(NPh)[NPh(SiMe2)]2-tacn], 5, that forms upon attack of Me2N- at one SiMe2 group. The formation of 5 is discussed on the basis of the interactions identified in solution. 相似文献
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M. T. Ganzerli-Valentini S. Meloni V. Caramella-Crespi P. A. Borroni 《Journal of Radioanalytical and Nuclear Chemistry》1976,34(1):103-112
The adsorption of about 50 ions on molybdenum dibromide, (Mo6Br8)Br4·2H2O, in nitric acid was investigated. The preparation of the adsorber and its characterization is presented and discussed. Adsorption
mechanism studies were carried out for some noble metals and chromium. Sorption cannot be ascribed to ion exchange mechanism
but to formation of insoluble species, and to settlement of few ions into surface sorption sites or into a limited number
of cavities in the cluster crystal structure of the adsorber. 相似文献
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《Analytical letters》2012,45(16):1255-1264
Abstract The DC polarographic behavior of the Cu(II)-inosine complex was investigated, in aqueous solutions of inosine in Britton Robinson buffer solutions at pH's from 1.0 to 4.0. At low concentrations of free inosine ion, only one polarographic wave was found corresponding to a two-electron reduction. Anisotropy of g/ = 2,039, g// = 2,287 and A// = 172G, A/= OG, was observed in the ESR spectrum of the Cu(II)/inosine complex. When the composition ratio of the complex was obtained by both polarography and ESR, it was found that the ratio Cu(II) to inosine was 1:2. The polarographic wave showed a two electron reduction wave. 相似文献
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Dr. Robert J. Baker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16258-16271
The chemistry of the uranyl ion ([UO2]2+) has evolved remarkably over the past few years, with unexpected reactivity observed that challenge our understanding of this ion, and of actinides in general. This review highlights some recent advances in the field, focussing on the organometallic chemistry of the uranyl moiety, which is not well developed in comparison to lower oxidation states of uranium. The use of uranyl as a catalyst is highlighted and the newly developed supramolecular chemistry is described. The uranyl oxygen atoms have been considered as inert, but recent work has shown that is not necessarily the case and is discussed herein. Finally, reduction to the [UO2]+ ion will be discussed. 相似文献
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Jiazeng Sun D. R. MacFarlane M. Forsyth 《Journal of polymer science. Part A, Polymer chemistry》1996,34(17):3465-3470
A series of poly(ethylene oxide-dimethyl siloxane) copolymers, — [SiMe2O(CH2CH2O)n]m — (n = 2, 3, 4, 5, 6.4, 8.7, 13.3), were synthesised by the reaction of polyethylene glycol with dimethyl dimethoxy/diethoxysilane. Corresponding ion-conductive polymers were prepared by complexing these copolymers with salts (sodium tetrafluoroborate or ammonium adipate). The highest conductivity of these systems at room temperature was 3 × 10−4 S cm−1 and 6 × 10−5 S cm−1, respectively. The glass transition temperature of these copolymers is reported and is seen to be dependent on the length of the ether units. The effects of siloxane content, salt concentration, and temperature on the conductivity are discussed. © 1996 John Wiley & Sons, Inc. 相似文献