Vibration spectra of rare earth metal tantalates

Infrared and Raman spectra of TRTa₇O₁₉ (TR = La, Nd, Eu) have been considered. Their structures have not been determined yet. Vibration spectra enable to assume the presence of TaO₄-tetrahedrons in tantalates. Vibration spectra of TRTaO₄ have been considered as well. Vibration spectra of TR₃TaO₇ have been recorded. Crystals of Le₃TaO₇, Nd₃TaO₇ are isostructural to veberite, while those of Eu₃TaO₇ to pyrochlorine. Factor-group analysis of the vibrations of the above samples of rare earth metal tantalates has been performed.     

Fusion temperatures of rare earth metal trihalides

The fusion temperatures (T _f) of rare earth metal trihalides LnX₃ (Ln=La–Lu, Y; X=Cl, Br, I) typically decrease to a minimum, before taking on an upward trend as the ionic radius of Ln³⁺ decreases. This trend is associated with the variations in the energetic stability of the coordination polyhedron around Ln³⁺. A good correlation is obtained between the variations in the energetic stability of the crystal structure of LnX₃ andT _f.

---

Zusammenfassung Die Schmelztemperaturen (T _f) der Trihalide der Seltenen Erdmetalle LnX₃ (Ln=La-Lu, Y; X=Cl, Br, J) gehen mit abnehmendem Ionenradius von Ln³⁺ auf typische Weise durch ein Minimum. Dieser Trend wird mit den Unterschieden in der energetischen Stabilität der um das Ln³⁺-Ion angeordneten Koordinationspolyeder in Verbindung gebracht. Es wurde eine gute Korrelation zwischen der energetischen Stabilität der Kristallstruktur undT _f erhalten.

---

LnX₃ (Ln=La-Lu,Y; =l,, I) . Ln³⁺. LnX₃ .

     

Surface-initiated group transfer polymerization mediated by rare earth metal catalysts

We present the first example of a surface-initiated group transfer polymerization (SI-GTP) mediated by rare earth metal catalysts for polymer brush synthesis. The experimentally facile method allows rapid grafting of polymer brushes with a thickness of >150 nm in <5 min at room temperature. We show the preparation of common poly(methacrylate) brushes and demonstrate that SI-GTP is a versatile route for the preparation of novel polymer brushes. The method gives access to both thermoresponsive and proton-conducting brush layers.     

Hydrogenation of carbon monoxide by tetranuclear rare earth metal polyhydrido complexes. Selective formation of ethylene and isolation of well-defined polyoxo rare earth metal clusters

The reaction of the tetranuclear rare earth metal polyhydrido complexes {Cp'Ln(mu-H)2}4(THF) (Cp' = C5Me4SiMe3, Ln = Y (1a), Lu (1b)) with carbon monoxide (1 atm) yielded ethylene and the corresponding tetraoxo cubane complexes (Cp'Ln)4(mu3-O)4 (Ln = Y (5a), Lu (5b)). Stepwise formation of some key reaction intermediates, such as oxymethylene complexes (Cp'Ln)4(mu-OCH2)(mu-H)6(THF) (Ln = Y (2a), Lu (2b)), enolate species (Cp'Y)4(OCH=CH2)(mu-O)(mu-H)5(THF) (3), and dioxo complex (Cp'Y)4(mu3-O)2(mu-H)4(THF) (4), was confirmed. The molecular structures of 2a, 4, and 5b were determined by X-ray diffraction studies.     

Generation of rare earth metal clusters by means of the gas-aggregation technique

Generation of rare-earth clusters is achieved using a gas aggregation technique. Varying the nucleation conditions induces a change in the relative cluster abundances. This can be understood in terms of competing cubic versus icosahedron structures.     

Catalysis of Ugi four component coupling reactions by rare earth metal triflates

Substoichiometric quantities of scandium and ytterbium triflate increase the yield of Ugi four component coupling reactions of aromatic aldehydes 2- to 7-fold. These rare earth metal triflates enhance the reaction yields primarily via activation of the imine intermediate of this multicomponent reaction.     

Developments of rare earth metal catalysts for olefin polymerization

This review article describes recent developments in rare earth metal complexes as polymerization catalysts, focusing on the polymerization of ethylene and α-olefins. Most of this kind of catalysts had been based on metallocene type complexes, and their catalytic behaviors are surveyed. Advanced series of half-metallocene and non-Cp type catalyst systems are also summarized.     

Phase diagrams for systems formed by manganese and rare earth metal oxides

We analyze the advantages and disadvantages of various methods for representing P-T-x diagrams of three-component systems and their fragments in various coordinates.     

Direct formation of beta-glycosides of N-acetyl glycosamines mediated by rare earth metal triflates

A direct, mild and efficient protocol for the preparation of beta-glycosides of N-acetyl glucosamine (GlcNAc) and N-acetyl galactosamine (GalNAc) has been developed using peracetylated beta-GlcNAc and beta-GalNAc as donors. All rare Earth metal triflate promoters screened were found to promote glycosylation with Sc(OTf)(3) being superior in terms of reaction rate. Simple alcohol glycosylation was found to proceed smoothly in refluxing dichloromethane, whereas higher temperatures under microwave conditions were needed to attain acceptable yields with less reactive, carbohydrate based glycosyl acceptors. The protocol developed was applied to provide the first example of direct chemical formation of a disaccharide using both GlcNAc as a glycosyl donor and acceptor. The alpha-acetate donor was found to be significantly less reactive than the corresponding beta-anomer necessitating higher reaction temperatures under which glycoside anomerisation was found to occur. It was established, that the anomerisation only took place in the presence of both Sc(OTf)(3) and acetic acid.     

Catalytic addition of terminal alkynes to carbodiimides by half-sandwich rare earth metal complexes

The catalytic addition of terminal alkynes to carbodiimides has been achieved for the first time by use of half-sandwich rare earth metal complexes, such as {Me2Si(C5Me4)(NPh)}Y(CH2SiMe3)(THF)2, which offers a straightforward, atom-economic route to the N,N'-disubstituted propiolamidines which contain a conjugated C-C triple bond, a new family of amidines which were difficult to prepare by other means. A rare earth metal amidinate species was confirmed to be a true catalytic species in this process, thus demonstrating for the first time that an amidinate unit, though being often used as an ancillary ligand for various organometallic complexes, can itself participate in a catalytic reaction under appropriate conditions.     

Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes

Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.     

辉光放电质谱法测定稀土矿中的15种稀土元素

利用高纯铜粉与稀土矿石粉末均匀混合压片制样.混合15种高纯稀土氧化物制样建立标准工作曲线,校正15种稀土元素相对灵敏度因子,再进行定量分析.结果 表明,稀土元素工作曲线的线性方程相关系数R2均大于0.996,相对标准偏差(RSD)小于5％,满足定量分析要求.测定结果与电感耦合等离子体质谱法(ICP-MS)和电感耦合等离...     

Thermal decomposition of some rare earth metal cupferrates and neocupferrates

The thermal decomposition of the eupferrates and neocupferrates of europium, terbium, dysprosium, holmium, erbium, and ytterbium was studied on the thermobalance. The metal chelates possessed poor thermal stability as well as a pronounced tendency to Coprecipitate reagent. The minimum oxide level temperatures for the metal cupferrates were : Eu, 570°; Tb, 540°; Dy, 550°; Ho, 610°; Er, 550° and Yb, 520°. The minimum oxide level temperatures for the metal neocupferrates were: Eu, 560°; Tb 565°; Dy, 540°; Ho,445°; Er, 530°; and Yb, 485°.     

稀土元素与NEB二元配合物的pH电位法分析

氨三乙氧基三苯甲酸(ＮＥＢ)(ＮＥＢ·ＨＣｌ的分子结构式见下图)作为有立体选择性的配体,它与铀酰离子ＵＯ2(Ⅱ)配位作用已有报导[1]。在对ＮＥＢ质子化常数及二元体系Ｍ(Ⅱ)-ＮＥＢ·ＨＣｌ(Ｍ=Ｃｄ、Ｃｏ、Ｎｉ、Ｃｕ和Ｚｎ)配合物的稳定常数测定的基础上[2],本文在25℃及离子强度为0 2ｍｏｌ/ＬＫＮＯ3的条件下,用精密ｐＨ电位法考察二元体系ＲＥ(ＩＩＩ)—ＮＥＢ(ＲＥ=Ｌａ→Ｎｄ,Ｓｍ→Ｌｕ,Ｙ)中存在的配合物物种及其稳定常数。ＮＥＢ·ＨＣｌ结构式1　实验部分1 1　试剂和仪器ＮＥＢ·ＨＣｌ(Ｈ3Ｌ·ＨＣｌ,Ｌ3-=Ｃ27Ｈ24ＮＯ9)…     

Extraction of rare earth elements by high molecular weight amines from nitric acid solutions

Extraction of trivalent rare earth elements by a high molecular weight primary amine /decylamine/ from 0.5–3M nitric acid solutions, containing potassium phosphotungstate /K₁₀P₂W₁₇O₆₁/, has been investigated. The effect of nitric acid and potassium phosphotungstate concentration of the organic solvent, and lanthanides ionic radii upon distribution coefficients has been studied. It has been established that decylamine solutions in chloroform can be used for the group isolation of rare earth elements and for their separation.     

Solubility of rare earth metal bromides and iodides in aqueous systems

Abstract  

The International Union of Pure and Applied Chemistry (IUPAC) project of collection, compilation, and critical evaluation of solubility data of bromides and iodides of the scandium group and all lanthanides in water and aqueous systems containing either halide acids, halide salts, or organic compounds is under preparation. As a result of their similarity to the chlorides, which were recently evaluated, the bromides and iodides in the lanthanide series should show some regularities in their solubility data. Unfortunately, the corresponding results show a large scatter when ordered according to the atomic number. Thus, it is complicated to select the best data for recommendation. Reasons for the inaccuracy of solubility measurements are outlined. In fact some solubility values of bromides predicted by correlation with chlorides seem to be more reliable than the experimental ones. As sufficient experimental data at various temperatures were available, the water-rich fragment of the LaBr₃–H₂O equilibrium phase diagram has been formed and depicted. It seems to be similar to the well-known LaCl₃–H₂O diagram. Several regularities, with respect to stoichiometry and solubility of compounds formed, were observed during investigations of the aqueous ternary systems. The complex iodides of various lanthanides display more regularities in their properties than the bromides do.