Pyridine-2-aldoxime complexes of rare earths

New complex compounds of some rare earths (samarium, europium, gadolinium, dysprosium and ytterbium) with the bidentate ligand pyridine-2-aldoxime have been prepared. Their absorption spectrum in the ultraviolet, visible and infrared regions have been recorded.     

Polarographic investigation of reduction process of some azodyes and their complexes with rare earths

The voltammetry behavior of six azodyes (tropeolin 0, tropeolin 00, tropeolin 000, magnezon, eriochrome black T, arsenazo I) with various structures of the interface circuit and substituents in o,o'-positions, and their rare earth (RE) complexes was investigated in detail. The process of complex formation of RE(III) with some o,o'-hydroxyazodyes was studied. The reduction mechanism of o,o'-disubstituted azodyes and their complexes with RE(III) was offered. It was confirmed that all investigated compounds and complexes are adsorbed on the surface of the dropping mercury electrode. The possibility of voltammetric determination of azodyes in a water environment was shown. The results of the research were used for determination of rare earths in inorganic materials.     

Chiral-at-metal complexes and their catalytic applications in organic synthesis

This tutorial review provides an introduction to the synthesis and characterization of chiral-at-metal complexes and their catalytic application in organic transformations. The synthetic access to these architectures either via chiral resolution or by employment of chiral ligands is described, characterization techniques for the complexes are referenced and the application of the R/S nomenclature is explained. Racemization and epimerization processes are often observed for the title compounds; the article gives mechanistic insights to these processes and describes how to recognize and document them. Finally, key catalytic applications in organic synthesis are presented and how the molecular architectures of the chiral-at-metal complexes lead to stereodifferentiation and, thus to enantiomeric excesses in the products.     

Spectrophotometric study and analytical applications of lanthanide-kojic acid complexes Direct determination of Nd, Ho and Er in mixtures of rare earths

The complexes of the rare-earth metals with kojic acid in weakly alkaline solution are reported. The characteristic absorbances of neodymium, holmium and erbium can be increased by factors of 4.3, 11.0 and 6.4 respectively, compared with those of the chlorides. The third-derivative spectra have been used to eliminate the interference of Ce, La and Y, and the sensitivities are again increased, by a factor of 6-9.     

Synthesis and solid-state structures of pyrazolylmethane complexes of the rare earths

In this paper, we report the first examples of trispyrazolylmethane complexes of rare earths. Reaction of LnCl3 with Tpm* (tris(3,5-dimethylpyrazolyl)methane) in THF or acetonitrile gives good yields of the [Ln(Tpm*)Cl3] (Ln = Y, Ce, Nd, Sm, Gd, Yb). Tpm* adducts of the lanthanide triflates [Ln(Tpm*)(OTf)3(THF)] (Ln = Y, Ho, Dy) may also be prepared. The X-ray crystal structures of [Y(Tpm*)Cl3], [Sm(Tpm*)Cl3(THF)], and [Ln(Tpm*)(OTf)3(THF)] (Ln = Y, Ho) are reported. The halide/triflate complexes may be used to prepare the aryloxide complexes [Ln(Tpm*)(OArMe2)3] (Ln = Y, Nd, Sm, Yb; ArMe2 = C6H3-2,6-(CH3)2), which are fluxional in solution as a result of interactions between the Tpm* and the aryloxide groups. The structures of the Nd and Sm complexes have been determined. Finally, the reaction of [Nd(BH4)3(THF)3] with Tpm* in THF results in the displacement of two THF molecules to give [Nd(Tpm*)(BH4)3(THF)]. Infrared spectra are consistent with tridentate borohydride coordination. The X-ray structures of these compounds indicate that the Tpm* ligand is less strongly bound than its anionic trispyrazolylborate analogues.     

吡咯基金属络合物的制备及其在有机合成中的应用

本文综述了近年来吡咯基金属络合物的研究进展, 详细讨论了σ~N-、σ~C-、π-型吡咯基金属络合物的制备方法, 以及各类吡咯基金属络合物在有机合成中的应用。     

稀土配合物导数吸收光谱的研究III.稀土离子-钛铁试剂配合物高阶导数光谱的研究及应用

研究了稀土离子-钛铁试剂水溶液体系的三阶及四阶导数光谱.在0.05-0.3mol.dm^-^3氢氧化钠溶液中,镨,钕,钐,镝,钬,铒,铥与钛铁试剂形成具有f-f跃迁吸收光谱的配合物.在紫外及可见区域内,它们各自有特征的吸收峰.其高阶导数光谱不仅灵敏度比常规吸收光增大了许多倍,且选择性也有很大的提高.如以峰-峰法测量四阶导数光谱,铒的导数摩尔吸光系数已达3.2x10^3L.moL^-^1.本文拟定了用稀土离子-钛铁试剂体系高阶导数光谱法测定混合稀土中镨,钕,钐,镝,钬,铒,铥的简便方法.和同类方法相比,本法具有灵敏度高,分析元素多,不需任何分离步骤和使用有机溶剂等优点.     

Direct spectrophotometric determination of rare earths in organic extracts with chlorophosphonazo III

The highly sensitive spectrophotometric determination of rare earths after extraction into di(2-ethylhexyl)phosphoric acid and trioctylamine is described. A sample of extract is diluted with n-butanol, the solution of chlorophosphonazo III in n-butanol is added, and the solution is made up to defined volume. Absorbance is measured at 660–665 nm against a reagent blank. The method is suitable for the study of the extraction of individual rare earths by different organic extrahents.     

Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

Activation analysis of rare earths : Separation of rare earths from accompanying elements

A scheme for the separation of rare-earth elements from gadolinite and tantalocolumbite minerals is discussed. The possibility of interference from traces of nonseparated elements in the subsequent separation of rare-earth elements from each other by cation exchange with α-hydroxyisobutyrate as the eluting agent is investigated.     

Removal, recovery, and recycling of triarylphosphonium-supported tin reagents for various organic transformations

Phosphonium-supported tin reagents and catalysts were prepared and were shown to be effective in Stille couplings, radical dehalogenations, radical cyclizations, and carbonyl allylations. Not only could the tin residues be removed from the crude reaction mixture through a phase separation process but also they could be recovered and recycled.     

Radiation-induced transformations of isolated organic molecules in solid rare gas matrices

The radiation-chemical behaviour of isolated organic molecules in solid rare gas matrices was studied using a combination of ESR and IR spectroscopy. The total radiation-chemical yields of degradation of organic molecules in solid argon and xenon were estimated. The effect of electron scavengers on the radiolysis of organic molecules in solid rare gases reveals that the main primary process is positive hole transfer from matrix to guest molecule. ESR spectra of a number of radical cations (alkanes, ethers, arenes) were characterized in a low-disturbing environment. It was found that the electronic characteristics (IP, polarizability) of the matrix used had crucial effect on trapping and reactions of the isolated radical cations.     

Electrodeposition studies of rare earths

The combination of neutron activation analysis (NAA) and electrochemistry has been used to study the deposition behavior of rare earth elements, as it is reported that excepting La, no other rare earths are electrodeposited. The radiotracers of rare earth elements were electrolyzed in an aqueous medium on a graphite electrode by varying the voltage and time of electrodeposition, thereby optimizing the final experimental conditions for quantitative deposition of rare earth elements. The observations are reported in this work.     

Raman scattering in rare earths tetraborides

The Raman spectra of single crystalline RE (rare earth) tetraborides REB₄ (RE = Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu) are measured and analysed with respect to the dependence of the phonon frequencies on the rare earth metal. Phonons representing octahedral B₆ units are identified by comparison to the according phonon modes of hexaborides. Their relative force parameters are estimated.     

Cyclam complexes and their applications in medicine

Cyclams are 14-membered tetraamine macrocycles which bind strongly to a wide range of metal ions. Medical interest has centred on clinical trials of a bicyclam for the treatment of AIDS and for stem cell mobilization, and on adducts with Tc and Cu radionuclides for diagnosis and therapy. Other potential applications particularly for Cr, Mn, Zn, and Ru cyclams are also emerging. We discuss in this critical review the mechanism of metal complexation, stability of metal cyclams and their structures, with particular emphasis on the variety of configurational states which metal cyclams can adopt. Understanding the factors which control the thermodynamics and kinetics of the interconversion of configurational states of metallo-cyclams may be a key factor in designing novel cyclam derivatives for future use in medicine.