Gas phase derivatization of endohedral metallofullerenes R@C-82 and R-2@C-80 (R = Nd, Ce)

Endohedral metallofullerenes Ce@C-82, Ce-2@C-80, Nd@C-82 and Nd-2@C-80 undergo gas phase ion/molecule reactions with the ion system from self-chemical ionization of vinyl acetate, and exohedral derivatives are thus generated, A new heterocycle is formed from metallofullerenes and a C2H3O+ cation, Endohedral metallofullerenes show much higher reactivities than empty fullerenes during the association and the charge and proton transfer processes, The strong electron-donating character of endohedral metallofullerenes is due to their unique super-atom-like electronic structures. (C) 1997 by John Wiley & Sons, Ltd.

Synthesis, crystal structure and magnetic properties of a series of polymeric lanthanoid-copper complexes [Ln(2)Cu(3){O(CH2-CO2)(2)}(6)].nH(2)O (Ln=La, Nd, n=9; Ln=Er, n=6)

The reaction of diglycolic acid, O(CH2CO2H)(2), with Cu(NO3)(2) . H2O and lanthanoid nitrate hydrate produces a series of novel Ln-Cu mixed metal complexes, [Ln(2)CU(3){O(CH2CO2)(2)}(6)]. nH(2)O (Ln = La, Nd, n = 9; Ln = Er, n = 6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln(3+) and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network.

多核Nd-Al双金属配合物对丁二烯的聚合 Ⅳ.烷基铝种类的影响

利用多核Ｎｄ－Ａｌ双金属配合物可单独引发双烯烃聚合的特点，考察了烷基铝种类对丁二烯加聚过程的影响，并与一般混合稀土催化体系进行了比较．烷基铝对活性体催化活性的影响与其用量有关，低ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序为：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＞Ａｌ（Ｃ８Ｈ１７）３＞ＡｌＢｕｉ３；高ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序相反：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＜Ａｌ（Ｃ８Ｈ１７）３＜ＡｌＢｕｉ３．烷基铝链转移作用强弱次序为：ＨＡｌＢｕｉ２≥ＡｌＥｔ３＞ＡｌＢｕｉ３＞ＡｌＭｅ３＞Ａｌ（Ｃ８Ｈ１７）３．根据聚丁二烯微观结构与其分子量的关系，可将烷基铝对聚丁二烯顺式含量的影响分为３类：（１）ＡｌＥｔ３和Ａｌ（Ｃ８Ｈ１７）３；（２）ＨＡｌ－Ｂｕｉ２和ＡｌＢｕｉ３；（３）ＡｌＭｅ３．所得结果有助于对稀土催化定向聚合过程的深入了解.

Nd~(3+)离子的晶场劈裂与基质晶体的化学键

利用研究复杂晶体化学键的理论方法，计算了一组ABO4型基质晶体的结构参数和化学键参数，发现Nd3+离子的总晶场劈裂能ΔE与晶体的平均共价性有线性关系.

非线性光学新材料K_2Ln(NO_3)_5.2H_2O(Ln=La,Ce,Pr,Nd,Sm)的晶体生长、结构和表征

非线性光学新材料Ｋ２Ｌｎ（ＮＯ３）５·２Ｈ２Ｏ（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ）的晶体生长、结构和表征董文庭张洪杰苏锵（中国科学院长春应用化学研究所稀土化学与物理开放实验室，长春１３００２２）Ｇｒｏｗｔｈ，ＳｔｒｕｃｔｕｒｅａｎｄＣｈａｒａｃｔ...

KCl-LiCl共晶熔体中Nd~(3+)和Ho~(3+)的电化学行为

用循环伏安法和恒电流电解后的电位时间曲线法，研究了ＬｉＣｌＫＣｌ熔体中Ｎｄ３＋和Ｈｏ３＋在Ｍｏ电极上的电化学行为。结果表明，Ｎｄ３＋和Ｈｏ３＋在Ｍｏ电极上的还原都为一步３电子可逆过程。其扩散系数分别为：１１３×１０－６和２１４２×１０－５ｃｍ２·ｓ－１（４５０℃），４５０℃下Ｈｏ３＋／Ｈｏ电极对的标准氧化还原电位为２９８７Ｖ（ｖｓ·Ｃｌ／Ｃｌ－１），并讨论了实验值较理论值偏负的原因。

Electrochemical behavior of molybdotungsate heteropoly complex with neodymium K10H3[Nd(SiMo7W4O39)(2)]xH(2)O in aqueous solution

The voltammetric behavior of the titled compound (denoted as Nd (SiMo7W4)(2)(13-)) in aqueous solution had been studied. An unusual pH response was discussed. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution were found. The electrocatalytic effects of the anion on the bromate reduction were investigated.

Electrochemical behavior of the molybdotungstate heteropoly complex with neodymium, K10H3[Nd(SiMo7W4O39)(2)]center dot xH(2)O in aqueous solution

The electrochemical behavior of the title compound (denoted Nd(SiMo7W4)(2)(13-)) in aqueous solution has been studied using cyclic voltammetry, sampled d.c. voltammetry, differential pulse voltammetry and bulk electrolysis with coulometry, The stable pH range of Nd(SiMo7W4)(2)(13-) is determined with UV-visible spectra. In the potential range between 0.70 and -0.45 V vs. SCE, the anion in pH 3.8 aqueous solution undergoes one-, one-, two- and two-electron steps of four redox processes attributed to electron addition and removal from the molybdate-oxo framework. The adsorption of the anion on the dropping mercury electrode and a self-inhibition influence of the adsorbed anions on the redox process of those anions dissolved in solution are found. The unusual dependence of the formal potentials on pH is explained with the competition of the protonation and ion-pair formation due to the high negative charge of Nd(SiMo7W4)(2)(13-) and its reduced forms. The electrocatalytic effects of the anion on the bromate are investigated.

The reactivity of lanthanide alkyl compounds with phenylacetylene: Synthesis and structure of [(Bu(t)Cp)(2)LnC CPh](2) (Ln=Nd, Gd)

[(Bu(t)Cp)(2)LnCH(3)](2) (Ln = Nd, Gd) react with PhC=CH to form the dimeric alkynide-bridged complexes [(Bu(t)Cp)(2)LnC=CPh](2) [Ln = Nd (I), Gd (II)]. Both compounds crystallized from toluene in the monoclinic space group C2/c. The two complexes are homologous, composed of asymmetric metal-alkynide bridges with Nd-C, Gd-C (alkynide) bond lengths of 2.602(4), 2.641(5) (I) and 2.532(6), 2.601(7) Angstrom (II), respectively. The average Nd-C (ring) and Gd-C (ring) distances are 2.746(13) and 2.703(19)Angstrom.

Relationship between the dissolution behaviours and current efficiencies of La, Ce, Pr and Nd in their chloride molten salts

The dissolution behaviours of La and Nd in their chloride molten salts were studied by means of the see-through cell, electrochemical weak polarization and quantum chemistry (extended Huckel molecular orbital). The reasons for the low current efficiencies of rare earth metals and the difference between La and Nd in their own chloride electrolytes on the basis of the solubility, rate of dissolution, and existing state of the metals dissolved as well as the structure of the melts, are discussed.

光折变Ce∶Nd∶LiNbO3晶体用于实时光学图象处理

Ｃｅ：Ｎｄ：ＬｉＮｂＯ３晶体具有优良的光折变性能，它作为全息记录介质，用于实现了光学图象微分和全息关联存储。

Nd（i－PrO）_2Cl－AlEt_3均相二元催化剂异戊二烯聚合动力学──Ⅲ．AlEt_3的链转移作用

Ｎｄ（ｉ－ＰｒＯ）_２Ｃｌ－ＡｌＥｔ_３均相二元催化剂异戊二烯聚合动力学──Ⅲ．ＡｌＥｔ_３的链转移作用蔡小平，龚志，王佛松朱行洁，李秀华（中国科学院长春应用化学研究所长春１３００２２）（吉林化工集团公司研究院吉林）关键词异戊二烯，聚合动力学，均相催化...

PREPARATION STRUCTURE AND PHYSICAL-PROPERTIES OF NEW SILVER LANTHANIDE MOLYBDENUM OXIDES [AGLNMO(2)O(8)(LN=LA-ND AND SM)]

We present the synthesis of AgLnMo(2)O(8) compounds with Ln = La-Nd and Sm. These compounds represent a scheelite-type structure characterized by MoO4- tetrahedrons. IR spectra show five absorption peaks in the region of 1000-400cm(-1), around 800cm(-1) and 400cm(-1), which correspond to the modes of the tetrahedral MoO42- groups. All of AgLnMo(2)O(8) (Ln = La-Nd and Sm) oxides are dielectric materials at room temperature. The temperature dependence of the magnetic susceptibility ofAgLnMo(2)O(8) (Ln = Ce-Nd and Sm) shows Curie-Weiss law behavior from 100K to 300K. This indicates that both Ce and Pr exist in +3 oxidation state in AgLnMo(2)O(8). For AgLaMo2O8, diamagnetic properties are found as expected.

SYNTHESES AND CRYSTAL-STRUCTURES OF (C8H8)ND(C5H9C5H4)(THF)(2) AND [(C8H8)GD(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)(2)]

LnCl(3) (Ln = Nd, Gd) reacts with C5H9C5H4Na (or K2C8H8) in THF (C5H9C5H4 = cyclopentylcyclopentadienyl) in the ratio of 1:1 to give (C5H9C5H4)LnCl(2)(THF)(n) (or (C8H8)LnCl(2)(THF)(n)], which further reacts with K2C8H8 (or C5H9C5H4Na) in THF to form the title complexes. If Ln = Nd the complex (C8H8)Nd(C5H9C5H4)(THF)(2) (a) was obtained: when Ln = Gd the 1:1 complex [(C8H8)Gd(C5H9C5H4)(THF)][(C5H8)Gd(C5H9C5H4)(THF)(2)] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)(2) (Ln = Nd or Gd), the Cyclopentylcyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp') in C5H9C5H4 group, cyclooctatetraenyl centroid (COT) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp', COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. - 0.0144 Angstrom).

Nd（OPr~i）_2Cl－AlEt_3均相二元催化剂异戊二烯聚合动力学Ⅰ．一般动力学研究

用膨胀计研究了Ｎｄ（ＯＰｒｉ）２Ｃｌ－ＡｌＥｔ３均相稀土催化剂异戊二烯聚合动力学．在实验条件下，本体系显示稳态聚合特征；聚合速度对单体浓度和催化剂浓度均为一级关系，即聚合速度方程为Ｒｐ＝Ｋｐ［Ｎｄ］［Ｍ］；本体系总的活化能Ｅａ为５７．４ｋＪ／ｍｏｌ．