La0.5R0.5Ba2Cu3O7,Pr0.5R0.5Ba2Cu3O7以及RBa2Cu3o7（R=稀土）的键共价性计

使用复杂晶体化学键理论计算了Ｌａ０．５Ｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｙ,Ｈｏ,Ｅｒ,Ｔｍ,Ｙｂ,Ｌｕ）（Ｌａ－Ｒ１２３）,Ｐｒ０．５Ｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｈｏ,Ｙ,Ｅｒ,Ｔｍ,Ｙｂ,Ｌｕ）（Ｐｒ－Ｒ１２３）以及ＲＢａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ,Ｈｏ,Ｙ,Ｅｒ,Ｔｍ）（Ｒ１２３）中Ｃｕ－Ｏ键的键共价性,结果表明Ｐｒ－Ｒ１２３,Ｌａ－Ｒ１２３,以及Ｒ１２３都应具有超导性,而实验结果是Ｌａ０．５Ｐｒ０．５Ｂａ２Ｃｕ０７,Ｒ０．５,Ｐｒ０．５Ｂａ２Ｃｕ３Ｏ７（Ｒ＝Ｌａ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ）无超导性,产生这种矛盾的原因尚不明确,需要做进一步的研究。     

ChemInform Abstract: A Structural Investigation of Hydrous and Anhydrous Rare‐Earth Phosphates.

Rhabdophane‐type LnPO₄·nH₂O (Ln: La, Nd, Sm, Gd, Dy) and xenotime‐type Ln′PO₄·nH₂O (Ln′: Y, Yb) are prepared by a precipitation‐based method and characterized by powder XRD and XANES.     

Zur Kenntnis des Verhaltens der Oxidsulfate der Seltenen Erden gegen Chlorwasserstoff. I. Umsetzung der Oxidsulfate einiger Seltener Erdmetalle mit Chlorwasserstoff

Reactions of the oxide sulphates M₂^IIIO₂SO₄ of La, Pr, Nd, Sm, Gd, Dy, Er, Yb and Y with hydrogen chloride between 450 and 600°C are described. The temperature dependence of reaction course is comparable with that of rare earth's oxides reactions with hydrogen chloride.     

Synthesis of heterobimetallic lanthanide <Emphasis Type="Italic">tert</Emphasis>-butoxides and their catalytic properties in reactions of CO<Subscript>2</Subscript> with epoxides

Heterobimetallic tert-butoxides (t-BuO)₅Cu₂Ln (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), (t-BuO)₅MLa (M = Mn, Fe, Co, Ni), (t-BuO)₅ZnNd, and (t-BuO)₄ZnFe were prepared in high yields by the reaction of t-BuOLi with a stoichiometric mixture of a lanthanide halide LnX₃ (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; X = Cl, I) and a d-transition metal salt MX_n (M = Zn, Cu, Mn, Fe, Co, Ni; X = Cl, Br). (t-BuO)₅Cu₂Ln (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) and (t-BuO)₅ZnNd at room temperature and atmospheric pressure induce copolymerization of CO₂ with cyclohexene oxide, affording the polycarbonate in a yield of 3–6 g g^–1 catalyst. The complex (t-BuO)₅FeLa, and also iron alcoholates (t-BuO)₂Fe and (t-BuO)2_Fe(bipy) under similar conditions catalyze the reaction of CO₂ with propylene oxide affording monomeric propylene carbonate in a yield of 35–45 g g^–1 catalyst.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1295–1299.Original Russian Text Copyright © 2004 by Nikitinskii, L. Bochkarev, Khorshev, M. Bochkarev.This revised version was published online in April 2005 with a corrected cover date.     

高锰酸稀土化合物的制备及性质

把CCl4中的Mn2O7加到稀土氧化物中制备了稀土高锰酸盐. 并测定了它们的化学组成, 研究了它们的红外光谱, 摩尔电导率, X射线粉末衍射及热谱性质试验了高锰酸镧对苯甲醇的氧化能力, 表明比高锰酸钾有更强的氮化能力.     

Sur de nouveaux composés oxygénés du cobalt +III dérivés de la perovskite

TCoO₃ phases where T is a rare earth (T = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) have been prepared under high oxygen pressure. LaCoO₃ is trigonal (space group $\text{R}\text{3}\text{c}$, D⁶_3d). NdCoO₃ is pseudo-tetragonal with the orthorhombic symmetry and the GdFeO₃ type structure as the following TCoO₃ phases. Crystallographic investigations at high temperature, magnetic and electric measurements on YCoO₃ and LuCoO₃ characterize a transition from the low spin to the high spin state of cobalt +III.     

Herstellung wasserfreier Thiocyanate der Seltenerdmetalle

Zusammenfassung Durch Umsatz der wasserfreien Chloride mit Kaliumthiocyanat in Tetrahydrofuran (THF) konnten erstmalig wasserfreie Thiocyanate von Seltenerdmetallen als kristalline, sehr hygroskopische Substanzen isoliert werden; ihre Löslichkeit und das Verhalten im Hochvakuum wurde untersucht. Sie besaßen die Zusammensetzung Ln(SCN)₃ · 4 THF (Ln=La, Ce, Pr, Nd, Sm, Gd, Dy, Y, Ho, Er) bzw. M(SCN)₃ · 3 THF ·C₆H₆ (M=Yb). Der Solvatäther wurde unterhalb 150° abgegeben wobei die solvatfreien Produkte resultierten.     

Extraction of rare earth elements with 2-[2'-(methoxydiphenylphosphoryl)phenyldiazenyl]-4-<Emphasis Type="Italic">tert</Emphasis>-butylphenol in the presence of 1-butyl-3-methylimidazolium and trioctylmethylammonium picrates

Extraction of micro amounts of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y with solutions of 2-[2'-(methoxydiphenylphosphoryl)phenyldiazenyl]-4-tert-butylphenol in 1,2-dichloroethane in the presence of 1-butyl-3-methylimidazolium and trioctylmethylammonium picrates has been studied. The stoichiometry of extracted complexes has been determined, the effect of HNO₃ concentration in aqueous phase on the efficiency of rare earth elements recovery into organic phase has been considered.     

Synthesis and powder X-ray diffraction analysis of new mixed rare-earth and selenium oxychlorides with composition LnSeO3Cl

A series of new mixed rare-earth and selenium oxychlorides with composition LnSeO₃Cl (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Y) were prepared by annealing together LnOCl and SeO₂ in sealed silica tubes. The resulting compounds were characterized by powder X-ray diffraction. The unit cell parameters of the phases were determined. Lanthanum—europium oxychlorides crystallized in the tetragonal system to give the Sillen phases analogously to tellurium compounds with the similar formula, whereas Tb—Yb and Y oxychlorides crystallized in the orthorhombic system. It is likely that the latter oxychlorides are not layered compounds.     

Herstellung von Seltenerdcyaniden

Zusammenfassung Seltenerd-cyanoargentateM[Ag(CN)₂]₃ wurden hergestellt (M=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er und Y), die aus wäßriger Lösung mit 3–4 Mol H₂O kristallisieren. Pr-cyanoargentat wurde entwässert und mit Li reduziert; hierbei konnte das in Tetrahydrofuran (THF) unlösliche Pr(CN)₃ im Gemisch mit anderen Stoffen erhalten werden. Da sich LiCN als inTHF löslich erwies, wurde die Herstellung aus AgCN und Li inTHF in Gegenwart von Naphthalin verbessert. LiCN wurde mit Seltenerdbromid-THF-Solvaten inTHF umgesetzt; hierbei fielen die bisher unbekannten einfachen Erdcyanide aus, die sehr zersetzlich sind und nach dem Trocknen die ZusammensetzungM(CN₃)· ·2THF besaßen (M=Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm Yb, Lu und Y). Die Umsetzung verläuft bei den Verbindungen der Ceriterden schwieriger als bei denen der Yttererden; die Cyanide von La und Ce wurden nur mit überschüssigemTHF erhalten.

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Rare-earth cyanoargentatesM[Ag(CN)₂]₃ were prepared (M=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Y), crystallising from aqueous solution with 3–4 moles of water. Pr-cyanoargentate was dehydrated and reduced with Li yielding some Pr(CN)₃, insoluble in tetrahydrofurane (THF), in mixture with other substances. Because LiCN proved to be soluble inTHF, the preparation from AgCN and Li inTHF in the presence of naphthalene was refined. LiCN was reacted with rare-earth bromide-THF-solvates inTHF, whereupon precipitation occured of the hitherto unknown, very sensitive to moisture simple rareearth cyanides, which after drying had the compositionM(CN)₃· ·2THF (M=Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y). The reaction is more difficult with the lighter lanthanon bromides than with the heavier ones; the cyanides of La and Ce were prepared only with excessTHF.

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邻氯苯甲酸稀土配合物的合成、表征及结构

本文合成了邻氯苯甲酸与十五种稀土的配合物REL~3·H~2O(RE=Y,La～Lu,L=Clc~6H~4CO~2H),研究了它们的热分解及红外光谱.测定了钕、铽及镥三种稀土的配合物晶体结构,均属单斜晶系,空间群P2~1/n,稀土离子配位数为9,配合物呈无限链状聚合结构.     

Synthesis and study of rare-earth uranogermanates

A series of M^III(HGeUO₆)₃ · 8H₂O rare-earth uranogermanates (M^III = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er) were prepared by precipitation from solutions under hydrothermal conditions. The compositions and structures of the synthesized compounds were studied, their complete crystallographic and functional similarity were established, and the processes of their dehydration and thermal decomposition were studied on the basis of chemical analysis, X-ray diffraction, IR spectroscopy, and differential scanning calorimetry data.     

Synthesis,characterization and tg-dsc study of lanthanide trifluoroacetate-2-azacyclononanone compounds

The synthesis, characterization and tg-dsc study of Ln(tfa)₃?·?3aza where Ln?=?La, Pr, Nd, Sm, Eu, Gd, Tb and Er, tfa?=?trifluoroacetate and aza?=?2-azacyclononanone are reported. The obtained X-ray powder diffraction patterns show that the compounds are divided in two isomorphous groups: La, Pr, Nd and Eu, Sm, Gd, Tb and Er. For all compounds, the thermodegradation under nitrogen gave the respective oxifluorides (LnOF) as the final product. The melting temperature intervals are 105–110°C, 100–112°C, 90–95°C, 79–101°C, 65–70°C, 75–90°C, 64–76°C and 50–65°C for the La, Pr, Nd, Sm, Eu, Gd, Tb and Er compounds, respectively, and it is verified that the lanthanide contraction induces a weaker intermolecular interaction between adjacent molecules in the solid state.     

Structural features of the crystalline iodide complexes of some rare-earth elements with carbamide and acetamide

New acetamide and carbamide complexes LnI₃ · 4Ur · 4H₂O (Ln = La, Eu, Dy, Ho, Y; Ur is carbamide) and LnI₃ · 4AA · 4H₂O (Ln = Nd, Eu, Dy, Ho, Y; AA is acetamide) are synthesized. The complexes are characterized by the data of chemical analysis, IR spectroscopy, and X-ray diffraction analysis. The ligands (water, carbamide, and acetamide molecules) are coordinated by the rare-earth element atoms through the oxygen atom, and the coordination polyhedron is a distorted square antiprism. The iodide ions are not coordinated and are located in the external sphere. The structural characteristics of the complexes are compared in the series [Ln(L)₄(H₂O)₄]I₃ (Ln = La, Nd, Eu, Gd, Dy, Ho, Er; L = AA, Ur).     

Syntheses, structures, optical and magnetic properties of Ba2MLnSe5 (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er)

The twelve quaternary rare-earth selenides Ba(2)MLnSe5 (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er) have been synthesized for the first time. The compounds Ba(2)GaLnSe(5) (Ln = Y, Nd, Sm, Gd, Dy, Er) are isostructural and crystallize in a new structure type in the centrosymmetric space group P ?1 of the triclinic system while the isostructural compounds Ba(2)InLnSe(5) (Ln = Y, Nd, Sm, Gd, Dy, Er) belong to the Ba(2)BiInS(5) structure type and crystallize in the noncentrosymmetric space group Cmc2(1) of the orthorhombic system. The structures contain infinite one-dimensional anionic chains (1)(∞)[GaLnSe(5)](4-) and (1)(∞)[InLnSe(5)](4-), and both chains are built from LnSe(6) octahedra and MSe(4) (M = Ga, In) tetrahedra in the corresponding selenides. As deduced from the diffuse reflectance spectra, the band gaps of most Ba(2)MLnSe(5) (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er) compounds are around 2.2 eV. The magnetic susceptibility measurements on Ba(2)GaGdSe(5) and Ba(2)InLnSe(5) (Ln = Nd, Gd, Dy, Er) indicate that they are paramagnetic and obey the Curie-Weiss law, while the magnetic susceptibility of Ba(2)InSmSe(5) deviates from the Curie-Weiss law as a result of the crystal field splitting. Furthermore, Ba(2)InYSe(5) exhibits a strong second harmonic generation response close to that of AgGaSe(2), when probed with the 2090 nm laser as fundamental wavelength.     

Composés d'addition des halogénures de niobium(V) et de tantale(V). V. Stabilité relative des composés des chlorures avec quelques oxydes et sulfures organiques

The adducts of niobium(V) and tantalum(V) chlorides with some aliphatic and cyclic oxides and sulfides, studied by NMR. spectroscopy in CHCl₃, are found to have 1:1 stoechiometry, at room temperature and lower. In the thioxane complex TaCl₅ · C₄H₈OS two species are present with the ligand coordinated by the sulfur atom or by the oxygen atom, respectively, in a proportion which has been determined. The thioxane adduct of niobium(V) chloride, however, is preferentially coordinated by the sulfur atom. There is also evidence for the species 2MCl₅ · C₄H₈OS. The relative basicity of each donor atom in dioxane, thioxane and dithiane is calculated and discussed. In contrast to the nitrile adducts, whose stability was found earlier to be controlled by inductive factors, the steric factors are more important for the ether and sulfide adducts: MCl₅ · Me₂X is more stable than the corresponding MCl₅ · Et₂X (M = Nb, Ta; X = O, S). Both niobium(V) and tantalum(V) chlorides have a soft behaviour, but NbCl₅ is a weaker Lewis acid than TaCl₅ and shows also a softer behaviour.     

Dynamic differential calorimetry of intermetallic compounds: II.Heats of formation,heats and entropies of fusion of rare earths-lead (REPb3) compounds

Dynamic differential calorimetry has been employed to evaluate the heats of formation, heats and entropies of fusion of REPb₃ compounds, where RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb. The results obtained have been estimated to be correct to within ±5–6‰ The general trend is a decrease in the heat of formation from La to Tm, which is correlated with the magnitude of the lanthanide contraction in these compounds.     

Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: II1). Synthesis and Structures of Ln(IO3)3 (Ln = Pr,Nd, Sm,Eu, Gd,Tb, Ho,Er) and Ln(IO3)3 · 2H2O (Ln = Eu,Gd, Dy,Er, Tm,Yb)

Single crystals of lanthanide iodates have been quickly grown by decomposition of the corresponding periodates under hydrothermal conditions. Single crystal X‐ray diffraction showed that two structure types form with the elements from Pr‐Yb, an anhydrous form for Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er and a dihydrate for Eu, Gd, Dy, Er, Tm, Yb. A detailed structure study is presented for one representative of each of these types, along with structure type and lattice parameters for the other materials. Tb(IO₃)₃: Space group P2₁/c, Z = 4, lattice dimensions at 120 K: a = 7.102(1), b = 8.468(1), c = 13.355(2)Å, β = 99.67(1)°; R1 = 0.034. Yb(IO₃)₃ · 2H₂O: Space group P1¯, Z = 2, lattice dimensions at 120 K: a = 7.013(1), b = 7.370(1), c = 10.458(2)Å, α = 95.250(5), β = 105.096(5), γ = 109.910(10)°; R1 = 0.024.     

Étude thermodynamique de la complexation des lanthanides trivalents avec l'acide hydroxyéthyl-éthylènediaminotriacétique et d'autres acides aminoacétiques : I. Détermination,par potentiométrie,des constantes d'acidité de certains acides aminopolyacétiques

Several polyaminoacetic acids have been studied by potentiometry at an ionic strength 1 (KCl) and 25° C, in order to determine their acidity constants. The pK values found are: 2.48, 9.67 (glycine); 1.84, 2.57, 9.27 (iminodiacetic acid); 1.03, 1.75, 2.31, 9.34 (nitrilotriacetic acid); 1.50, 1.95, 2.45, 6.21, 9.79 (ethylenediaminetetraacetic acid). The pK values of the lanthanide complexes Ln—EDTA—H are: 3.1, 2.14, 2.03, 1.89, 1.82, 1.44, 1.35, 1.27, 1.19, 1.17, 1.15 (Ln = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu).