Cationic complexes of Eu(III) and Sr(II) with diphosphine dioxides in organic extracts

IR spectroscopy was used to study the structure and composition of Eu(III) and Sr(II) complexes formed by cation-exchange extraction of these metals from their aqueous nitrate solutions with dichlorethane solutions of mixtures of chlorinated cobalt(III) dicarbollide (CCD) as a superacid with diphenyldiphosphine dioxides containing a methyl (Me-DPDO), ethyl (Et-DPDO), or polyoxyethylene bridge between two phosphorus atoms of phosphine oxide groups. At molar ratios DPDO/CCD ≤ 1, [Eu(H₂O)_nL₄]³⁺ complexes are formed in organic phases, whereas with an excess of DPDO relative to CCD, Eu(NO₃)L ₄ ²⁺ complexes are formed, where L = Me-or Et-DPDO. Polyoxyethylenediphosphine dioxide forms anhydrous complexes of composition Eu:L = 1:1 and 1:2 with Eu(III) and outer-spheric complexes of composition Sr:L = 1:1 and 1:2 with Sr(II), where the organic ligand molecules envelop the hydrated Sr(H₂O) _n ²⁺ cation. The peculiarities of extraction of the complexes are explained based on data about their composition and structure.     

Addition of nitriles to alkaline earth metal complexes of 1,2-bis[(phenyl)imino]acenaphthenes

Compounds [Sr(dpp-bian)(thf)4] (2), [Ba(dpp-bian)(dme)2.5] (3) and [Mg(dtb-bian)(thf)2] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp-bian)(thf)3], 3, and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)2] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)2] (7), respectively. The reaction of 2 with CH3C[triple chemical bond]N in THF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}2] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)3] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand.     

Influence of the texture of chromia catalysts on their activity in synthesis of 2-methylthiophene

The texture of Cr₂O₃-K₂O/Al₂O₃catalysts containing oxides of rare earth elements (REE) was studied. The catalysts are used for the synthesis of 2-methylthiophene by the reaction of H₂S with n-pentane or piperilene. The heterocyclization of n-pentane is a consecutive reaction involving a step of dehydrogenation of initial hydrocarbon. At this step the texture of the catalyst affects the yield of 2-methylthiophene. The yield of 2-methylthiophene obtained from piperilene and I₂S is independent of the catalyst texture.     

负载稀土型酸活化膨润土的酯化催化活性

负载稀土型酸活化膨润土的酯化催化活性李永绣，冯天泽，胡平贵，何小彬，辜子英，廖荣辉（南昌大学化学系南昌３３００４７）关键词稀土，膨润土，催化酯化可用稀土、膨润土单独作酯化催化剂，但活性不高［１～３］。本文将稀土用离子交换的方法负载到酸活化膨润土中，寻...     

醇盐法制备稀土化合物超微粉末

稀土元素具有广泛的用途,在大多数的应用中其效果都与原料的纯度、粒度、粒经分布范围等因素有关。由于超微粉末的比表面积大、化学活性高,因此可以预料,若将稀土化合物制成超微粉末,会使它的催化性能及在各种材料中的性能有明显的改变,也可使稀土有新的、更高的应用价值。     

Separating Ag, B, Cd, Dy, Eu, and Sm in a Gd matrix using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction chromatography for ICP-AES analysis

The separation procedure for Ag, B, Cd, Dy, Eu and Sm as impurities in Gd matrix using ICP-AES technique with an extraction chromatographic column has been developed. The spectral interference of the Gd matrix on the elements was eliminated using a chromatography technique with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) as the mobile phase and XAD-16 resin as the stationary phase. Ag⁺, B₄O₇²⁻, and Cd²⁺ were eluted with 0.1 M HNO₃, while rare earth ions were not. The best eluent for separating Eu and Sm in the Gd matrix was 0.3 M HNO₃. The limit of quantitation for these elements was 0.6-3.0 ng mL⁻¹. The recovery of Ag, B, and Cd was 90-104% using 0.1 M HNO₃ as the eluent, while that of Eu, Gd, and Sm ranged from 100 to 102% with 0.3 M HNO₃. Dy was recovered quantitatively with 4 M HNO₃. The relative standard deviation of the methods for a set of three replicates was between 1.0 and 15.4% for the synthetic and standard Gd solutions. The proposed separation procedure was used to measure Ag, B, Cd, Dy, Eu, and Sm in a standard Gd solution.     

钇对金属陶瓷力学性能和组织的影响

研究了添加钇对Ｔｉ（Ｃ，Ｎ）基金属瓷力学性能和组织的影响。结果表明，加入适量的钇能提高Ｔｉ（Ｃ，Ｎ）基金属陶瓷的抗变强度和硬度，其原因是由于钇与杂质硫起反应在化合物，净化了陶瓷相－金属相，陶瓷相－陶瓷相界面提高子界面结合强度     

铕掺杂BaPbO3的EXAFS研究

采用扩展Ｘ射线吸收精细结构方法，研究了铕掺杂ＢａＰｂＯ３多晶粉末中Ｅｕ，Ｐｂ两种原子的近邻结构。Ｅｕ的掺杂，导致八面体中金属Ｐｇ，Ｅｕ的配位数降低。     

钇对Ti-1100高温钛合金热稳定性和蠕变行为的影响

量了Ｔｉ１１００和Ｔｉ１１００／０１％Ｙ（质量分数）高温钛合金在６００℃／１００ｈ空气中暴露后的拉伸性能及在６００℃／１５０ＭＰａ／１００ｈ条件下的蠕变性能，利用透射电镜观察了合金室温及蠕变后的组织。结果表明，Ｔｉ１１００合金加入０１％的Ｙ后，由于原始β晶粒得到细化，明显改善了其热稳定性；固溶在基体中的硅原子阻碍位错滑移和攀移，使蠕变中的回复过程难于实现；稀土还抑制α２相的长大，所形成的氧化物也阻碍位错的运动。这些均有利于提高Ｔｉ１１００合金的抗蠕变性能。     

π－烯丙基稀土配合物的合成、结构及其催化烯烃聚合反应机理的研究 Ⅲ．LiLn（π－C_3H_5）_4·nD催化异戊二烯和苯乙烯均聚合反应的研究

本文研究了ＬｉＬｎ（π－Ｃ_３Ｈ_５）_４·ｎＤ（Ｌｎ＝Ｌａ、Ｔｂ，ｎ＝３；Ｌｎ＝Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｒ，ｎ＝２；Ｌｎ＝Ｙ、Ｄｙ，ｎ＝２．５；Ｄ为二氧六环）催化异戊二烯和苯乙烯的均聚合反应．其中，钇配合物的催化活性为最高．聚异戊二烯顺式－１，４链节含量在４３－８１％．聚合体系内少量给电子体的加入使聚合物中３，４－链节含量高达８４％．所得聚苯乙烯为无规结构．