含磺酸金属-有机配合物的研究

金属—有机配合物是目前功能配合物研究的热点。本文简述了磺酸的配位化学及含磺酸的金属有机配合物的研究概况,介绍了目前研究最多的几种含磺酸的金属—有机配合物,并对含磺酸的金属有机配合物的研究前景作了展望。     

含磺酸金属一有机配合物的研究

金属一有机配合物是目前功能配合物研究的热点。本文简述了磺酸的配位化学及含磺酸的金属有机配合物的研究概况，介绍了目前研究最多的几种含磺酸的金属一有机配合物，并对含磺酸的金属有机配合物的研究前景作了展望。     

钇掺杂的铕三元配合物的制备及其性能研究

应用Claisen酯缩合反应机理,合成了新型含有β-二酮结构的有机配体1,5-二苯乙烯基乙酰丙酮(Dsacac),并将其作为第一配体,1,10-邻菲罗啉(Phen)作为协同配体,分别合成Eu(Ⅲ)单核稀土配合物(Eu(dsacac)3phen)和Eu/Y不同质量比掺杂配合物(EuxY1-x(dsacac)3phen),分析了单核稀土配合物和掺杂配合物的结构、稳定性、荧光性能以及配合物的能量传递过程。结果表明,掺杂适量的非荧光离子Y3+可以提高配合物的发光强度。     

钇掺杂的铕三元配合物的制备及其性能研究

应用Claisen酯缩合反应机理,合成了新型含有β-二酮结构的有机配体1,5-二苯乙烯基乙酰丙酮(Dsacac),并将其作为第一配体,1,10-邻菲罗啉(Phen)作为协同配体,分别合成Eu(Ⅲ)单核稀土配合物(Eu(dsacac)3phen)和Eu/Y不同质量比掺杂配合物(EuxY1-x(dsacac)3phen),分析了单核稀土配合物和掺杂配合物的结构、稳定性、荧光性能以及配合物的能量传递过程。结果表明,掺杂适量的非荧光离子Y3+可以提高配合物的发光强度。     

芳香羧酸（苯基多羧酸）配合物研究进展

介绍了苯二甲酸、苯三甲酸、苯四甲酸等为配体的芳香羧酸配合物的配位模式,如苯二甲酸根据取代位置的不同,有对苯二甲酸,间苯二甲酸,邻苯二甲酸,与一元羧酸相比,配体中两个羧基的存在使得这些配体的配位模式更趋多样化,从而更有利于构筑高维结构的配位聚合物。综述了近几年芳香羧酸配合物的研究进展,表明芳香羧酸在组装超分子结构和合成配位聚合物方面有着突出的优势,特别是在金属有机配合物中占有重要地位。     

含茂基有机配合物的合成及表征

对含茂基有机配合物的合成及表征进行了简单介绍,例举了包括含茂基和四苯基卟啉基钇的有机金属配合物的合成,以及其他类型的有机配合物的合成,藉此探讨一般有机物配合物的合成与表征的共通性。     

新型二维层状配合物的构筑、表征及其荧光性能研究

4′-[4-甲基-6-(1-甲基-1H-苯并咪唑-2-基)-2-丙基-1H-苯并咪唑基甲基]联苯基-2-羧酸(HL)是一种含多个配位点和具有不同配位模式的氮杂环羧酸有机柔性配体,将其与Ag盐自由组合后,合成了磁性、荧光、分子分离、催化、吸附及胶粘剂助剂用新型金属有机配合物{Ag_2(HL)_2(SO_3CF_3)_2}_n,并对其结构和光致发光性能进行了分析。研究结果表明:该配合物是二维层状结构;与配体相比,室温时该配合物表现出较弱的荧光特性(发生了荧光淬灭现象),并且荧光发射峰位置与配体基本相同。     

含能配合物的研究进展

含能配合物是开发具有钝感、含能、环保材料的一个重要发展方向。概述了以高能多氮直链化合物如碳酰肼,富氮杂环化合物如三唑、四唑类为配体的配合物的合成、热行为以及性能的研究情况,同时简要地从分子或原子结构描述了一些其他多氮含能配体如肼、肼基甲酸甲酯等所形成的配合物的晶体结构以及热分解行为,并对含能配合物的发展方向进行了展望。     

稀土有机配合物的研究与应用

稀土金属配合物因镧系离子独特的电子结构而成为一类具有特殊性能的发光材料,有着重要的理论意义及应用价值。本文综述了光致发光稀土有机配合物的发光机理、发光特性以及有机配体研究等发展情况,针对光致发光稀土有机配合物发光材料在分析化学、生物、医药中的应用进行了综合性的评述,展望了稀土配合物发光的发展趋势。     

稀土有机配体的研究进展

综述了近年稀土有机配合物的主要配体种类及其对应稀土配合物的制备方法,包括β-二酮类配体、羧酸类配体、邻菲罗啉类配体和三苯基氧膦类配体。同时对稀土配合物在光电材料、生物医学工程及传感器等领域的应用前景进行了分析与展望。研制稳定性好、荧光量子效率更高的新型稀土配合物体系将是新一代稀土有机配体的追求目标。     

基于巯基嘧啶类衍生物构筑配合物的研究进展

巯基嘧啶及其衍生物配体是一类含有S原子的杂环有机化合物,它不论是在配位方面还是在活性方面都有很广泛的研究。自20世纪70年代末开始合成这类配体的第一个配合物,在以后的几十年里此类配合物的合成一直是研究的热点。本文主要就巯基嘧啶及其衍生物类配体的种类、配位方式进行了综述,指出巯基嘧啶及其衍生物类配体在化学和医学上得到了科学家的普遍关注,列举了这类配体构筑配合物的应用,并对其发展前景作了展望。     

基于巯基三氮唑及其衍生物构筑配合物的研究进展

巯基三氮唑是一种含硫氮杂环有机化合物,由于具有多个配位点和较强的配位能力以及衍生物的多样性, 近些年在配位化合物、医药等方面受到广泛研究。本文按照取代基数目的不同将巯基三氮唑衍生物分为疏基三 氮唑、单取代巯基三氮唑、多取代巯基三氮唑、多臂巯基三氮唑衍生物,并按照分类系统地总结了近些年来这 类配体及其金属配合物的合成方法和结构特征方面的研究成果,同时介绍了其金属配合物在药物、功能材料方 面的应用。最后依据巯基三氮唑及其衍生物构筑配合物的研究现状,从配体、金属离子两方面对巯基三氮唑未 来的研究方向进行了展望。     

Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: synthesis and catalytic applications

Transition metal complexes are indispensable tools for any synthetic chemist. Ideally, any metal-mediated process should be fast, clean, efficient, and selective and take place in a catalytic manner. These criteria are especially important considering that many of the transition metals employed in catalysis are rare and expensive. One of the ways of modifying and controlling the properties of transition metal complexes is the use of appropriate ligand systems, such as pincer ligands. Usually consisting of a central aromatic backbone tethered to two two-electron donor groups by different spacers, this class of tridentate ligands have found numerous applications in various areas of chemistry, including catalysis, due to their combination of stability, activity, and variability. As we focused on pincer ligands featuring phosphines as donor groups, the lack of a general method for the preparation of both neutral (PNP) and anionic (PCP) pincer ligands using similar precursor compounds as well as the difficulty of introducing chirality into the structure of pincer ligands prompted us to investigate the use of amines as spacers between the aromatic ring and the phosphines. By introduction of aminophosphine and phosphoramidite moieties into their structure, the synthesis of both PNP and PCP ligands can be achieved via condensation reactions between aromatic diamines and electrophilic chlorophosphines (or chlorophosphites). Moreover, chiral pincer complexes can be easily obtained by using building blocks obtained from the chiral pool. Thus, we have developed a modular synthetic strategy with which the steric, electronic, and stereochemical properties of the ligands can be varied systematically. With the ligands in hand, we studied their reactivity towards different transition metal precursors, such as molybdenum, ruthenium, iron, nickel, palladium, and platinum. This has resulted in the preparation of a range of new pincer complexes, including various iron complexes, as well as the first heptacoordinated molybdenum pincer complexes and several pentacoordinated nickel complexes by using a controlled ligand decomposition pathway. In addition, we have investigated the use of some of the complexes as catalysts in different C-C coupling reactions: for example, the palladium PNP and PCP pincer complexes can be employed as catalysts in the well known Suzuki-Miyaura coupling, while the iron PNP complexes catalyze the coupling of aromatic aldehydes with ethyl diazoacetate under very mild reaction conditions to give selectively 3-hydroxyacrylates, which are otherwise difficult to prepare. While this Account presents an overview of current research on the chemistry of P-N bond containing pincer ligands and complexes, we believe that further investigations will give deeper insights into the reactivity and applicability of aminophosphine-based pincer complexes.     

Synthesis of Schiff Base‐Ruthenium Complexes and Their Applications in Catalytic Processes

The synthesis of various Schiff base mononuclear and binuclear ruthenium complexes, whose additional ligands around the metal core have been selected from an array of motifs, is described. These types of ruthenium complexes, conveniently prepared from commonly available ruthenium sources, are rather stable, display good tolerance towards diverse organic functionalities and also to air and moisture. Remarkably, they exhibit a high activity and chemoselectivity in a variety of catalytic processes such as ring‐closing metathesis (RCM), Kharasch addition, alkyne dimerization, enol ester synthesis, ring‐opening metathesis polymerization (ROMP) and atom‐transfer radical polymerization (ATRP). This review covers both homogeneous and heterogeneous hybrid Schiff base‐ruthenium complexes.     

Chiral diphosphine and monodentate phosphorus ligands on a spiro scaffold for transition-metal-catalyzed asymmetric reactions

The preparation of chiral compounds in enantiomerically pure form is a challenging goal in modern organic synthesis. The use of chiral metal complex catalysis is a powerful, economically feasible tool for the preparation of optically active organic compounds on both laboratory and industrial scales. In particular, the metals coordinated by one or more chiral phosphorus ligands exhibit amazing enantioselectivity and reactivity. Many chiral phosphorus ligands have been synthesized and used in transition-metal-catalyzed asymmetric reactions in past decades. However, a large number of reactions still lack effective chiral ligands, and the enantioselectivities in many reactions are substrate-dependent. The development of effective chiral phosphorus ligands, especially ligands having novel chiral backbones, is still an important task in the area of asymmetric catalysis. Molecules containing a spirocyclic framework are ubiquitous in nature. The synthesis of molecules with this spiro structure can be traced back to 100 years ago. However, the use of this spirocyclic framework to construct chiral phosphorus ligands is a recent event. This Account outlines the design and synthesis of a new family of chiral spiro phosphorus ligands including spiro diphosphines and spiro monodentate phosphorus ligands with 1,1'-spirobiindane and 9,9'-spirobifluorene backbone and their applications in transition-metal-catalyzed asymmetric hydrogenation and carbon-carbon bond formation reactions. The chiral spiro diphosphine lgands SDP with a 1,1'-spirobiindane backbone and SFDP with a 9,9'-spirobifluorene backbone, and the spiro monophosphorus ligands including phosphoramidites, phosphites, phosphonites, and phospholane with a 1,1'-spirobiindane backbone were synthesized in good yields from enantiomerically pure 1,1'-spirobiindane-7,7'-diol and 9,9'-spirobifluoren-1,1'-diol. The ruthenium complexes of chiral spiro diphosphine ligands proved to be very effective catalysts for asymmetric hydrogenations of ketones, alpha-arylaldehydes and alpha,beta-unsaturated acids. The rhodium complexes of chiral spiro monophosphorus ligands are highly enantioselective for the asymmetric hydrogenations of alpha- and beta-dehydroamino acid derivatives, alpha-arylethenyl acetamides and non- N-acyl enamines. The spiro monophosphorus ligands were demonstrated to be highly efficient for the Rh-catalyzed asymmetric addition of arylboronic acids to aldehydes and N-tosylarylimines, Pd-catalyzed asymmetric allylation of aldehydes with allylic alcohols, Cu-catalyzed asymmetric ring opening reactions with Grignard reagents, and Ni-catalyzed asymmetric hydrovinylation of styrene derivatives with ethylene. The chiral spiro phosphorus ligands show high enantioselectivities for a wide range of transition-metal-catalyzed asymmetric reactions. In most of these transformations, the enantioselectivities of spiro phosphorus ligands are superior to those obtained by using the corresponding phosphorus ligands with other backbones. These results arise from the intriguing chiral inducement of spiro structures of the ligands.     

Trends in the chemistry of mono- to multimetal π-arene complexes of chromium and manganese

The preparation and the features of the ring activation in π-arene metal (chromium, manganese) complexes are discussed. The bottom-up approach to the synthesis of σ, π-bi- and multimetal complexes, and the synthesis of cyclometallated and multicyclic complexes from a variety of selected routes are also reviewed. The stereochemical features of such complexes, and their applications in carbon–carbon coupling reactions and metal insertion reactions are highlighted. The redox reactivities and selected applications of (multi)metal π-arene complexes in catalysis and organic synthesis are included. Finally, the extension of the multimetal π-arene complexes to larger assemblies is shown. The importance of arene ring substituents in the basic mononuclear units and their use as bidentate metalloligands, with bidentate amines as linkers, in the construction of polymers, metal organic frameworks, networks (also on nanoparticles or silica supports), is highlighted.     

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT

A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.     

丙烯酰胺衍生物及其应用

丙烯酰胺及其衍生物容易自聚或与其他烯类单体共聚而得到不同结构和性能的聚合物.对发展中的丙烯酰胺衍生物进行了总结,并分别介绍含磺酸基、N-烷基取代、N-芳基取代以及含有酮结构的多种丙烯酰胺衍生物的性能及其在不同领域的应用.     

Effect of ozone and ozone/activated carbon treatments on genotoxic activity of naphthalenesulfonic acids

Naphthalenesulfonic compounds are widely used, mainly by the textile industry in the synthesis of azoic colorants. The presence of the sulfonic group is known to endow these compounds with high water‐solubility and low biodegradability, although its influence on their genotoxic activity is unknown. The use of energetic oxidants is recommended for the degradation of organic compounds which are refractory to biological treatment. Ozone and ozone/activated carbon have been proposed as the best alternatives to remove these compounds. The results showed that the more sulfonic groups there are on the aromatic ring of this family of contaminants, the lower is their genotoxic activity. All the compounds studied presented genotoxic activity at elevated concentrations. Ames test results indicate that DNA damage was produced by substitution of nitrogenated bases. The system based on the combined use of ozone and activated carbon was the most efficacious in the depuration of water containing these contaminants. This approach rapidly degraded the naphthalenesulfonic acids, eliminated their genotoxic activity and reduced their organic material content using low doses of ozone. © 2002 Society of Chemical Industry     

Preparation of polyacrylic dyes

Polyacrylic chloride was reacted with aminonaphthol sulfonic acid to give a polymeric intermediate, from which the corresponding dyestuff was prepared by coupling with an aromatic diazonium salt. The water-solubility of the polymeric azo dye was found to depend mainly on the number of sulfonic groups in the molecular chain, and the colouring of dye was comparatively rich in variety. A copolymer of acrylic chloride with methyl methacrylate was directly reacted with a dyestuff containing amino groups to give a polymeric dye. In the molecular chain of those polymeric dyes, the functional structure of the dyestuff was kept by its incorporation to the acrylic polymer chain.