Some new water-soluble phosphines with the involvement of the trivalent rare earth ion

The new type of water-soluble phosphine with the involvement of the trivalent rare earth ion, TPPTS·Ln (Ln=Eu, Dy, Er, Tm, Yb, Lu; and TPPTS=tris (m-sulfonatophenyl) phosphine), were synthesized from the precursor TPPTS·Na₃ and oxides of rare earth. The chemical composition of TPPTS·Ln was determined by elemental analysis and ICP-AES. IR, Raman showed that the sulfonate group in the complexes was a tridentate ligand.³¹P NMR, TG-DTA, molar conductivity and the fluorescence of these complexes were also recorded and discussed. Chen Xinlan, born in 1946, Associate Professor     

Inorganic-organic hybrids constructed of bis（undecatungstogerma- nate）lanthanates polyoxoanions and oxalate-bridged dinuclear copper complexes and their magnetic properties

A series of inorganic-organic hybrids K₂Na _m H_9−m [{Ln(GeW₁₁O₃₉)₂}{Cu₂(bpy)₂(μ-ox)}]·nH₂O (bpy = 2,2-bipyridine and ox = oxalate; Ln = La, Nd, Sm, Eu, Gd; n = 19, 17, 22, 20, 19; m = 4, 4, 4, 9, 2) were isolated after reacting in a potassium acetate buffer. X-ray structural analyses show that compounds 1–5 are isomorphic and consist of [Ln(GeW₁₁O₃₉)₂]¹³⁻ polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure. The 1D chain further connects into the 3D framework by π-π interactions with neighboring bpy groups. The magnetic susceptibility data indicate that antiferromagnetic coupling between the neighboring Cu²⁺ ions in the structure and the rare earth ions affects magnetic property of the structure.     

Synthesis and relaxivity of polycarboxylic hydrazone rare earth complexes——Relaxivity of α-oxo-pentanedioic acid benzoyl hydrazone Gd-complexes

Synthesis of ligand, α-oxo-pentanedioic acid benzoyl hydrazone (H₂LPB), and its six rare earth (La, Pr, Nd, Sm, Gd and Er) complexes are reported. The composition and the properties of the complexes were characterized by element analysis, thermal analysis, UV, IR and¹H NMR spectra. Besides, relaxivity (R ₁) of Gd-complex has been determined by INVREC.Au program, using inversion recovery pulse sequences, R₁=8.05 mmol · L⁻¹ · s⁻¹. The acute toxicity of Gd-complex in animal has also been tested, and the median lethal dose (LD₅₀) is equal to (468.2±30) mg/kg.     

氯化稀土与丙氨酸固体配合物的研究

在水相介质中制得６个氯化稀土与丙氨酸的配合物,通式为ＬｎＣｌ３·Ｌ·６Ｈ２Ｏ和ＬｎＣｌ３·３Ｌ·ｎＨ２Ｏ（Ｌｎ为Ｎｄ,Ｄｙ,Ｙｂ;Ｌ为丙氨酸）。通过化学分析、元素分析、红外光谱、热重分析及Ｘ光粉末衍射等方法对这些配合物进行了物理化学性质及结构表征。     

1-苯基-3-甲基-5-氧代吡唑-4-基乙醛酸稀土配合物的合成及表征

在pH=6～7的乙醇-水溶液中,合成了9个1-苯基-3-甲基-5-氧代吡唑-4-基乙醛酸稀土配合物。元素分析确定了配合物的组成为Ln_2A_3·H_2O(Ln=La,Pr,Nd,Sm,Eu,Tb,Er,Yb和Y,A为配体)。通过摩尔电导,紫外光谱、红外光谱,核磁共振谱以及差热分析对配合物进行了表征,认为配体为四齿配体,配合物具有双核结构。     

Investigation on the coordinate structures of the rare earth metal complexes with edta and cydta ligands

0　IntroductionThegreatattentionhasbeenpaidtorareearthorradioactiverareearthmetalcomplexesfortheirvariousbiologicactivi ties[1 3] .Forexamples,theradioactiverareearthmetal1 53SmⅢ com plexeswerewidelyusedfortumourtherapyofbrain ,liver,lung ,heartandbonetissues[4 5] ;forrareearthmetalEuⅢandTbⅢemitinguniquefluorescence ,theircompoundswereappliedfordiagnosesofvariousdiseases[6 ,7] ;forrareearthmetalGdⅢcontainingthemosthigh spinsingleelectrons,itscomplexeswereusuallyusedforcontrastagentsofmag…     

Raman and infrared spectroscopic investigation of some hydrous LnTPPTS complexes (Ln=La,Sm)

The Raman and IR spectra of LnTPPTS·10H₂O [Ln=La,Sm, TPPTS=P(m-C₆H₄SO₃) ₃ ³⁻ ] complexes are reported. Based on the observed Raman and IR characteristic frequencies, a vibrational assignments has been made for these complexes. Coordination induces a lengthening of the S−O bonds and a shortening of the C−S bond. The C−S stretching frequencies should therefore increase while the position of the should move to a lower wavenumber. Vibrational modes of metal-oxygen polyhedron V _(La-O) at 146, 168,253 cm⁻¹ are the structural charactrization for coordinate bond of LnTPPTS complexes. Chen Zhenhua: Born in 1938, Professor     

Synthesis and characterization of N-aryloxo-functiona- lized β-ketoiminate rare-earth complexes and their catalytic activity for the polymerization of ε-caprolactone

The synthesis and characterization of dimeric rare-earth amides stabilized by a dianionic N-aryloxo functionalized ,8-ketoiminate ligand are described. Reactions of 4-（2-hydroxy-5-methyl-phenyl） imino-2-pentanone （LH2） with Ln[N（SiMe3）2]3（μ-Cl）Li（THF）3 in a 1：1 molar ratio in THF gave the dimeric rare-earth amido complexes [LLn{N（SiMe3）2}（THF）]2 [Ln = Nd （1）, Sm （2）, Yb （3）, Y （4）]. These complexes were well characterized, and the definitive molecular structures of complexes 3 and 4 were determined. It was found that complexes 1-4 can initiate the ring-opening polymerization of ε-caprolactone, and the ionic radii of the central metals have significant effect on the catalytic activity.     

稀土烯丙基化合物的研究(XV)——含环戊二烯基或吡咯基的异核混配型稀土烯丙基配合物的合成

以２－甲基烯丙基氯化镁与无水稀土氯化物低温下反应,得到含镁２－甲基烯丙基稀土配合物（Ｌｎ（Ｃ４Ｈ７）２（Ｍｇ２Ｃｌ５（ＴＨＦ）４）．该配合物与环戊二烯或吡咯进行配体取代反应,分别得到两个系列的含环戊二烯基（Ｃ５Ｈ５）或吡咯基（Ｃ４Ｈ４Ｎ）的异核混配型稀土烯丙基配合物（Ｌｎ２（Ｃ５Ｈ５）３（Ｃ４Ｈ７）Ｍｇ３Ｃｌ８（ＴＨＦ）６,Ｌｎ２（Ｃ４Ｈ４Ｎ）３（Ｃ４Ｈ７）Ｍｇ３Ｃｌ８（ＴＨＦ）６（Ｌｎ＝Ｃｅ,Ｐｒ,Ｎｄ））．这２个配合物均经元素分析、红外光谱、质谱鉴定及摩尔电导的测定     

Well-defined bis（phenolate） lanthanide methoxides as efficient initiators for the polymerization of cyclic carbonate and lactide

Lanthanide methoxides supported by carbon-bridged bis(phenolate) ligands 2,2′-methylene-bis(6-tert- butyl-4-methylphenoxo) (MBMP2-) [(MBMP)Ln( μ-OMe)(THF)2]2 (Ln = Nd (1), Yb (2)) were synthesized in high yields by the protolysis reaction using (C5H5)3Ln(THF) as starting materials, and complex 1 was structurally characterized. The coordination geometry around the center metal can be best described as a distorted octahedron. Complexes 1 and 2 were shown to be efficient initiators for the ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) and L-lactide. The mechanism of DTC polymerization was explored by the end group analysis of the oligomer.     

四（对－羟基苯基）卟啉稀土配合物的固相合成与表征

在固相条件下合成了4种四（对－羟基苯基）卟啉稀土（Ln^3 =La^3 ,Pr^3 ,Nd^3 ,Dy^3 ）配合物,用元素分析,ICP,紫外可见光谱,红外光变进行表征,并用循环伏安法研究了配合物的电化学 性质,实验结果表明：稀土卟啉配合物的电化学性质相似,在循环伏安图中,出现了三对氧化还原峰,第一对为[C44H22N4O4Ln(III)]^ /[C44H28N4O4Ln(II)],第二对为[C44H28N4O4Ln(II)]/[C44H28N4O4Ln(I)]^-,第码对为[C44H28N4O4Ln(I)]^-/[C44H28N4O4Ln]^2-.     

稀土烯丙基化合物的研究（Ⅺ）──钆、镝、钬、铒和镱的镁烯丙基四甲基乙二胺配合物的合成

低温时，以四甲基乙二胺（ｔｍｅｄ）作稳定剂，用无水稀土氯化物与烯丙基氯化镁在四氢呋喃中反应，合成了对空气和湿气相当敏感的稀土镁烯丙基四甲基乙二胺配合物（Ｃ３Ｈ５）２ＬｎＣｌ５Ｍｇ２（ｔｍｅｄ）２（Ｌｎ＝Ｇｄ，Ｄｙ，Ｈｏ，Ｅｒ，Ｙｂ）配合物的组成经元素分析、红外光谱、质谱等鉴定以及摩尔电导的测定．还进行了配合物与二氧化碳或含活泼氢的化合物的反应．     

稀土氧化物掺杂对TiO2/沸石光催化性能的影响

以钛酸丁酯和稀土氧化物为原料, 采用溶胶 凝胶法制备了镧、 钕和镱稀土离子掺杂TiO₂/沸石光催化剂. 通过XRD和IR方法对样品进行表征, 研究了不同沸石粒径及不同稀土氧化物掺杂量(质量分数)对农药敌敌畏光催化降解性能的影响. 结果表明, 当沸石最佳粒径为0.15 mm, La³⁺掺杂量质量分数为3.0%时（以TiO₂质量计）, 稀土离子的掺杂可显著提高TiO₂//沸石的光催化降解性能.     

磁控溅射表面镀膜对Nd2Fe14B稀土永磁体抗腐蚀性能的影响

在Nd₂Fe₁₄B稀土永磁体基体表面,采用磁控溅射（直流+射频）技术制备了Ti/Ni,Ti/Al和Al/Ni等二元合金薄膜和Ti/Al/Ni三元合金薄膜。并通过中性盐雾试验、腐蚀失重计算、电化学腐蚀试验、金相观察等方式,对比研究了不同表面处理对Nd₂Fe₁₄B稀土永磁体基体抗腐蚀性能的影响,并构建了腐蚀模型。研究发现：Ti/Ni,Ti/Al和Al/Ni等二元合金薄膜和Ti/Al/Ni三元合金薄膜均有效地提高了Nd₂Fe₁₄B稀土永磁体基体耐中性盐雾腐蚀和电化学腐蚀的能力;Ti/Al/Ni三元合金薄膜较Ti/Ni,Ti/Al和Al/Ni等二元合金薄膜有更优良的综合耐腐蚀性能,其磁控溅射工艺参数为：Ar流量60 sccm,基片温度常温,Ni,Al,Ti的溅射功率都为250 W,基片转速20 r·min^-1,镀膜均速0.3 nm·s^-1,总计溅射时间1 h。     

NMR and IR investigations of ternary inclusion complexes among β-cyclodextrin, rare earth metal ions, and naphthalenediamines

Ternary inclusion complexes β-cyclodextrin (β-CD), rare earth metal ions (YbCl₃, YCl₃), and 1,8-naphthalene- diamine/1,5-naphthalenediamine are synthesized in basic aqueous media, which are characterized via ¹H NMR and IR spectroscopy. The stoichiometric proportion of β-CD:YbCl₃:1,5-naphthalenediamine is 2:1:2, that of β-CD:YCl₃:1,8-naphthalenediamine is 2:1:1, and that of β-CD:YbCl₃:1,8-naphthalenediamine is 2:1:1. The IR spectroscopy of the ternary inclusion complexes in the range of 935–1 000 cm⁻¹ reveals the existence of the coordinate bond M—O or M—N. The possible conformations of the ternary inclusion complexes are depicted. Biography: JIANG Huiming(1972–), male, Associate professor, research direction: molecular complex chemistry, supramolecular chemistry.     

香兰素对甲苯胺希夫碱硝酸稀土配合物的合成

制备了香兰素(3-甲氧基-4-羟基苯甲醛)对甲苯胺希夫(Schiff)碱硝酸稀土配合物。该配合物由一个中心稀土离子,二个单齿配位希夫碱,二个双齿配位硝酸根和一个外界硝酸根组成,中心稀土离子的配位数是6,其一般式为[LnL_2(NO_3)_2]NO_3(Ln=La, Ce, Pr, Nd, Sm, Eu; L=希夫碱配体)。     

稀土烯丙基化合物的研究(ⅩⅢ)──重稀土2-甲基烯丙基1,2-二甲氧基乙烷配合物的合成

用无水重稀土氯化物与2-甲基烯丙基氯化镁在四氢呋喃（THF）中于低温下反应，合成了对空气和湿气极为敏感的四个未见报道的化合物．经元素分析、红外光谱、质谱及电导的测定，确定化合物的组成为（C4H7）2LnCl3Mg（DME）2（Ln=Y，Ho，Er和Yb；式中DME为1，2-二甲氧基乙烷）．以同样方法采用轻稀土化合物进行合成，则可得到一组轻稀土化合物（C4H7）2LnCl5Mg2（DME）2（Ln=La，Pr，Nd，Sm和Gd）．     

中稀土硝酸盐与甘氨酸固体配合物的研究

文中以１：４摩尔比在水中制得了中稀土硝酸盐与甘氨酸固体配合物，经过化学分析，元素分析、红外光谱、热谱及Ｘ光粉衍射等方法，确定配合物通式 为Ｌｎ（Ｎｏ３）３（Ｇｌｙ）４（Ｌｎ＝Ｓｍ．Ｅｕ，Ｇｄ．Ｔｂ．Ｄｙ．Ｅｒ；Ｇｌｙ＝Ｇｌｙｃｉｎｅ），并对所制配合物某些物理性质及化学性质进行了讨论。     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.