稀土络合催化苯乙烯-马来酸酐配位共聚

本文首次应用稀土配位催化剂NdL_3-A1(i-Bu)_3,在苯溶剂中,50℃下使苯乙烯-马来酸酐共聚,制得富于交替,数均分子量高达6—8.5×10~5的白色粉末共聚物。系统地研究了共聚合反应的特征及动力学行为,共聚合反应具有低的表现活化能(10.5kJ/mol),并且不被对苯二酚所阻聚。不同配体稀土(钕)催化剂活性次序为:Nd(naph)_3>Nd(P_(507))_3～NdCl_3·6H_2O>Nd(P_(204))_3>Nd(acac)_3·3H_2O,并且,初步揭示了共聚合反应的机理——两种单体形成电荷转移络合物参与增长的配位共聚。     

THE POLYMERIZATION OF ACETYLENE BY COORDINATION CATALYSTS COMPOSED OF NEODYMIUM COMPOUND, ALUMINUM TRIALKYL AND A THIRD COMPONENT

This paper describes the polymerization of acetylene by coordination catalysts composed ofvarious neodymium compounds, (Nd (P_(204))_3; Nd (P_(507))_3; Nd (NO_3)_3 3P_(350); Nd (BA)_3.2H_2O; andNd (acac)_3.2H_2O), aluminum trialkyl and an electron donor. The catalysts show fairly high catalyticactivity and high cis stereospecificity on acetylene polymerization at 30℃.     

环己酸钕配合物的合成和结构研究

本文合成了Nd(C_6H_(11)COO)_3·2C_2H_5OH(NdA_3·2C_2H_5OH)和Nd(C_6H_(11)COO)_3·2H_2O(NdA_3·2H_2O),用X射线衍射法测定了前者的晶体结构。它为单斜晶系,P_1~-空间群,晶胞参数如下:a=1.2625(6)、b=1.2385(6)、c=0.9421(5)nm;α=91.69(4)、β=98.49(4)、γ=99.16(5)°;ν=1.436nm~3;Z=2。经最小二乘法修正,最终结构偏差因子R为0.0866。每个钕原子都通过两个双齿和两个三齿羧基与另两个钕原子相联形成线状聚合物,另有一个双齿螯合的羧基和两个乙醇分子与其配位。钕的配位数为9。对二者的红外光谱和热分析也进行了研究。     

氯化钕与二甲亚砜配合物的晶体结构

[Nd(DMSO)_5(H_2O)_3]Cl_3·H_2O的单晶用ENRAF-NONIUS CAD 4型四圆衍射仪收集衍射数据进行结构分析,最终偏离因子R=0.036。晶体属三斜晶系空间群P_1,晶胞参数a=9.800(1),b=10.531(1),c=14.757(2);α=93.07(1),β=100.2l(1),γ=99.71(1)°;Z=2。结构分析证实:晶胞中有二个[Nd(DMSO)_5(H_2O)_3]Cl_3·H_2O分子。Nd与五个DMSO及三个H_2O中的氧形成八配位的畸变三角十二面体结构。Cl~-与络阳离子通过离子键相互作用。[Tb(DMSO)_5(H_2O)_3)Cl_3·H_2O的晶胞参数与之相近,有类似的结构。     

无机过氧化物的研究——Ⅱ.从粉状白钨酸制备过氧钨酸钕

应用倒滴加法制备的粉状白钨酸,制备了两个新的不同组成的过氧钨酸钕:NH_4NdW_2(O_2)_5(OH)_2·4H_2O(1)和NH_4NdW_3(O_2)_3O_8·6H_2O(2)并对化合物的一些性质进行了表征。     

硝酸二(α-羟基异丁酸)二水合钕的合成、表征及晶体结构

合成的标题配合物Nd(C_4H_7O_3)_2·NO_3·2H_2O晶体属C2/c空间群,晶胞参数:a=0.8996(1)nm,b=0.8601(1)nm,c=2.1111(3)nm,β=92.38(1)°Z=4,晶体中配合物呈聚合链状结构,硝酸根无序分布在靠近对称中心的2个相关位置,钕的配位数为8。     

希土元素与苯甲酰三氟丙酮的螯合物

用三种方法制备了两类希土和苯甲酰三氟丙酮的固体螯合物Ln(BTA)_4·Hpip(Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er及Y)和Ln(BTA)_3·2H_2O(Ln=Nd,Eu及Tb).测定了Nd(BTA)_4·Hpip的分子量和Ln(BTA)_4·Hpip的熔点.研究了Nd(BTA)_4·Hpip,Sm(BTA)_4·Hpip和Nd(BTA)_3·2H_2O的热稳定性,并与相应的苯酰丙酮螯合物进行了比较.     

稀土络合催化环氧乙烷聚合

以稀土化合物-二(2-乙基己基)膦酸钕[Nd(P_(204)_3],三异丁基铝和水组成的络合催化剂,引发环氧乙烷聚合.结果表明,稀土络合催化剂是制备高分子量聚环氧乙烷的新型催化剂.聚合反应速度与环氧乙烷浓度呈一级关系,与Nd(P_(204))_3浓度呈一级关系.聚合的总活化能E_α=33.8kJ/mol,表观速率常数K_p=1.67×10~(-3)s~(-1)·mol~(-1)·1     

水合1-苯基-3-甲基-4-三氟乙酰基吡唑酮-5(HPMTFP)与铕(Ⅲ)配合物的晶体结构

[Eu(PMTFP)_3·(H_2O))2)·H_2O的单晶用ENRAF-NONIUS CAD4型四圆衍射仪收集衍射数据进行结构分析。最终偏离因子R=0.046。晶体属空间群P2_1/a。晶胞参数a=16.055(2),b=16.016(3),c=17.752(5),β=106.41(2)°,Z=4。结构分析证实,Eu与配体的六个氧以及二个水分子中的氧形成八配位的稍畸变三角十二面体结构。氢键是连按配位分子形成晶体的主要键力,[Nd(PMTFP)_3·(H_2O)_2]·H_2O单晶的晶胞参数与之相近,有类似的分子与晶体结构。     

含氧桥的笼状化合物[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)-[H_3O]~+·1/2(CH_3)_2NCHo·1/2H_2O的合成和结构

[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O(DMF=(CH_3)_2NC-HO)(M_r=1204.67)的晶体属三斜晶系,空间群P,晶胞参数a=16.438(6);b=22.22(1);c=11.325(5),α=104.25(4);β=108.97(3);γ=97.68(4)°,V=3688(3),Z=4,D_c=2.17gcm~(-1),R=0.056,R_w=0.074,晶胞中每个不对称单元含有两个[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O,阴离子[Mo_5P_2O_(23)]~(6-)中的Mo、P原子成一个畸变五角双锥构型。有一个阴离子的所有原子(Mo、P、O)位置完全确定,而另一个阴离子有一个磷酸根的三个氧原子位置出现二重位置统计分布。化合物的阳离子为二甲胺阳离子和水合氢离子。     

Photoacoustic spectroscopy study of neodymium complexes with alanine,valine, phenylalanine and tryptophan

Neodymium complexes with amino acids: Nd(Ala)(3)Cl(3).3H(2)O, Nd(Val)(3)Cl(3).3H(2)O, Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O (Ala: L-alanine, Val: L-valine, Phe: L-phenylalanine, Trp: L-tryptophan) are synthesized and their photoacoustic (PA) spectra are reported. The nephelauxetic ratio beta, bonding parameter b(1/2) and Sinha parameter delta are calculated based on their PA spectra. The variation of these parameters and correlation of them with the nature of metal-ligand bonding are discussed. The PA intensity analysis of the f-f transitions of neodymium ion is carried out by calculating the intensity branching vector. The environmental effect on the f-f transitions of neodymium ion is also studied. The branching vectors of the f-f transitions of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O are similar, which indicates the perturbation of the two ligand fields is similar. The branching vectors of energy levels 4G(5/2)+(2)G(7/2) of Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O increase remarkably compared with those of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O. As the degree of covalency increases, the oscillator strength of the hypersensitive transition exhibits a corresponding increase. The relaxation process of Nd(Ala)(3)Cl(3).3H(2)O is established through its PA and electron absorption spectroscopy (EAS). A method used to resolve the PA amplitude spectrum is suggested. With the phase spectrum, PA absorption bands of Nd(Trp)(3)Cl(3).3H(2)O are resolved well in the region of ligand absorption.     

Water-free neodymium 2,6-naphthalenedicarboxylates coordination complexes and their application as catalysts for isoprene polymerization

A series of four coordination polymers based on neodymium have been hydrothermally synthesized with different carboxylic acids as a linker. The structures of the compounds Nd(2)(2,6-ndc)(3)(H(2)O)(3)·H(2)O (1), Nd(2)(2,6-ndc)(2)(ox)(H(2)O)(2) (2), and Nd(2,6-ndc)(form) (3) (2,6-ndc = 2,6-naphthalenedicarboxylate; ox = oxalate; and form = formate) have been determined by single-crystal X-ray diffraction analysis. They exhibit rather dense networks built up from infinite chains of NdO polyhedra connected to each other through the 2,6-ndc ligand. Terminal and bridging aquo species are present in the coordination sphere of Nd for 1, whereas some of them are partially replaced by oxalate groups in 2 and fully substituted by formate groups in 3. The water-free phase 3 as well as the compound Nd(form)(3) (4) were considered for catalytic reaction for polymerization of isoprene in the presence of Al-based cocatalyst, affording cis-polyisoprene with good conversions. Residual Nd material with unchanged structure was found in the polymeric material. The neodymium luminescence of compounds 3 and 4 was also measured.     

镧系(Nd3+、Ho3+、Er3+)与1-苯基-3-甲基-4-三氟乙酰基吡唑酮-5和二安替吡啉甲烷三元配合物的研究

用分光光度法对镧系离子(Nd~(3+),Ho~(3+),Er~(3+))与1-苯基-3-甲基-4-三氟乙酰基吡唑酮-5(PMTFP)和二安替吡啉甲烷(DAM)水-乙醇溶液体系的研究以及对制备钕的相应配合物的元素分析证实:形成的三元配合物的的组成比为Ln~(3+):PMTFP:DAM=1:3:1。计算了相应配合物超灵敏跃迁的光吸收振子强度,并图示了它们之间的线性关系。研究了固态钕的三元配合物的红外吸收光谱和热稳定性。 镧系离子(Ln~(3+))同DAM和1-苯基-3-甲基-4-苯甲酰基吡唑酮-5(PMBP)等β-二酮以及Ln~(3+)与PMTFP和三辛基磷氧化物(TOPO)的三元配合物的研究已有报导。本文报导了Ln~(3+)(Nd~(3+)、Ho~(3+)、Er~(3+))-PMTFP-DAM体系中的超灵敏跃迁现象与配位作用,以及Nd(Ⅲ)-PMTFP-DAM配合物的合成、组成和性质。     

Synthesis, characterization of neodymium chloride complex of amine-bis(phenolate) ligand and its reactivity in the ring-opening polymerization of ε-caprolactone

The neodymium chloride complex[Nd（ONN’O）Cl（THF）]₂ supported by amine-bis（phenolate） ligand was synthesized by the metathesis reaction of anhydrous NdCl₃ with Li₂（ONN’O）[H₂ONN’O = Me₂NCH₂CH₂N（CH₂-3-Bu₂^t-5-Me-C₆H₂OH）₂]in high yield.X-ray structural determination shows[Nd（ONN’O）Cl（THF）]₂ complex consists of two seven-coordinate neodymium centers linked throughμ-Cl bridges.And this complex was successfully used to initiate the ring-opening polymerization（ROP） ofε-caprolactone.     

CRYSTAL STRUCTURE OF NEODYMIUM（Ⅲ）COMPLEX WITH1，2，4—BENZENETRICARBOXYLIC ACID

<正> [NdC6H3(COO)3(H2O)3]·H2O, Mr=423. 45, orthorhombic,space groupP212121,a=6. 120(3) ,b=9. 719(2) ,c=20. 133(8) A ,V=1197. 5A3.Z = 4,F (000) = 820,DC=2. 35g/cm3,μ(Moka) = 44. 1cm-1.The final R = 0. 0278 and Rw= 0. 0270 for 1760(I>3σ(I)) observed unique reflections. The neodymium ion is nine-coordinated by six oxygen atoms of carboxylato groups from four 1, 2, 4-benzenetricar-boxylates and three aqua molecules,forming a distorted monocapped square antiprism. The Nd -O distances fall in the range of 2. 41 - 2. 70A with an average of 2. 51A     

Structure and mesomorphism of neodymium(III) alkanoates

The structural and thermal behavior of all members of the homologous series of neodymium(III) alkanoates, ranging from neodymium(III) butyrate to neodymium(III) eicosanoate are described. Neodymium(III) butyrate monohydrate, Nd(C3H7COO)3.H2O crystallizes in space group P1 (No. 2), Z = 2. The lattice parameters are a = 9.824(2) A, b = 11.974(2) A, c = 14.633(2) A, alpha = 86.21(2) degrees, beta = 75.92(2) degrees, gamma = 77.97(2) degrees. The crystal structure consists of ionic layers of neodymium ions, separated by bilayers of butyrate anions. In the ionic layers, the neodymium ions are connected by bridging tridentate carboxylate groups to zigzag chains, whereas the chains are connected among themselves by bridging bidentate carboxylate groups. The two crystallographically different neodymium ions are both having coordination number 9, with a geometry close to a monocapped square antiprism. The structure of the higher homologues can be derived from the structure of neodymium butyrate by extending the alkyl chains. These compounds have a lamellar bilayer structure with planes of neodymium(III) ions coordinated to the carboxylate groups and with the alkyl chains in an all-trans conformation. All homologous compounds from neodymium(III) pentanoate to neodymium(III) pentadecanoate display a thermotropic mesophase, which was identified by high-temperature X-ray diffraction as a smectic A phase. For the series from neodymium(III) pentanoate to neodymium(III) undecanoate an additional high viscosity mesophase is present between the crystalline state and the smectic A mesophase.     

Spectroscopic properties of neodymium(III)-containing polyoxometalates in aqueous solution

The spectroscopic properties of the neodymium(III)-containing polyoxometalates (POMs) [Nd(PW(11)O(39))(2)](11-), [Nd(PMo(2)W(9)O(39))(2)](11-), [Nd(PMo(4)W(7)O(39))(2)](11-), [Nd(PMo(6)W(5)O(39))(2)](11-), [Nd(SiMo(2)W(9)O(39))(2)](13-), [Nd(P(2)W(17)O(61))(2)](17-), [NdW(10)O(36)](9-), [NdP(5)W(30)O(110)](12-) and [NdAs(4)W(40)O(140)](25-) are described. Absorption spectra of aqueous solutions of the complexes have been recorded and the transition intensities are parameterised in terms of the Judd-Ofelt intensity parameters Omega(lambda) (lambda=2, 4, 6). Marked differences were found between the luminescence lifetimes of the complexes of the type Nd(POM) and those of the type Nd(POM)(2), due to a better shielding of the neodymium(III) ions from the bulk water molecules in the latter type of complexes.     

Synthesis and Crystal Structure of Neodymium Complex with Glycine [Nd(Gly)(H_2O)_7]Cl_3

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两个具一维水链的镧系配位聚合物的合成与晶体结构(英文)

以Ln2O3(Ln=Nd和La),2,2′-联吡啶-3,3′-二羧酸(bpdc),4,4′-联吡啶(bpy)为原料,采用溶剂热法合成了2个具有二维骨架结构的无机-有机杂化材料[Nd2(bpdc)3(H2O)2]·bpy·4H2O(1)和[La2(bpdc)3(H2O)4]·4H2O(2),通过IR和X-射线单晶衍射分析等手段对其结构进行了表征。晶体1属于单斜晶系,C2/c空间群,晶胞参数a=3.3104(7)nm,b=0.74812(15)nm,c=1.9848(4)nm,β=104.75(3)°。晶体2属于单斜晶系,C2/c空间群,晶胞参数a=2.6749(5)nm,b=0.71165(14)nm,c=2.0542(4)nm,β=92.70(3)°。在这2个配位聚合物中,晶体中的结晶水沿着b轴呈现一维无限有序排列,将化合物中二维的金属有机骨架通过氢键相连进而形成了三维超分子结构。