希土离子不对称双氮杂冠醚配合物的合成、表征及CD谱

在乙醇中合成出三个希土硝酸盐与冠醚(+)-12,17-二乙基-1,4,7,10-四氧杂-13,16-二氮杂环十八烷(L)的配合物。经元素分析确定其组成为［Ln(NO₃)₂·L(+)］NO₃(Ln=La, Pr, Nd)。通过UV-VIS和FI-IR、电导测定等方法研究了配合物的配位结构和性质。测定并讨论了手性配合物［Pr(NO₃)₂·L(+)］NO₃的CD谱。     

希土元素与β-丙氨酸席夫碱双核配合物的合成、表征及催化活性

合成了未见报道的九种希土元素与水杨醛缩-β-丙氨酸(H₂L)的双核配合物。元素分析及摩尔电导值等表明此系列新配合物组成为［Ln₂(HL)₃NO₃］(NO₃)₂·nH₂O，［Ln=La,Pr, Nd, Sm, Gd，n=2; Ln=Tb, Er, Yb, Y, n=4］，钆、钇的配合物分属轻、重希土组。运用热重-差热分析、紫外及红外光谱、核磁     

［Ln(EO2)3］(ClO4)3·3H2O的晶体结构研究

合成了希土高氯酸盐开环冠醚二缩乙二醇(EO2)晶体，(Ln=Nd, Ho)，测定了结构，文内以Nd-L的数据为主要研究对象(方括号内是Ho-L的数据)。晶体属单斜晶系，P2₁/n空间群，化学式［Ln(EO2)₃］(ClO₄)₃·3H₂O，晶胞参数为：a=14.124(1)［14.087］, b=13.990(1)［14.039］, c=15.265(1)［15.014］?; β=95.78(1)［95.64］°; V=3001.1(6)［2955］?³; Mr=815.01［835.70］; Z=4; Dc=1.804［1.865］g/cm³；石墨单色器，μ(MoKα)=2.09［3.07］ mm^-1，最终偏离因子R=0.055［0.074］, R_W=0.071［0.109］。研究结果表明晶体具有相同的结构，配位多面体为九配位三帽三棱柱。发现EO2醚链有绕C-C键呈STT分布的规律。弱配体高氯酸根不参加配位。     

稀土二膦酸配合物的合成、结构和荧光性质

合成并表征了3个同构的稀土二膦酸化合物Ln(hpyedpH₂)(hpyedpH₃)·2H₂O [Ln=Gd (1)，Eu (2)，Tb (3)；hpyedpH₄=1-hydroxy -2-(3-pyridyl)ethylidene-1，1-diphosphonic acid，C₇H₁₁NO₇P₂]，测定了化合物1的单晶结构。发现它们具有链状结构，其中Ln通过3个或4个O-P-O基团交替连接，链与链之间存在氢键和π-π堆积作用。探讨了化合物2和3的荧光性质。     

［Ln(DMSO)7Cl］［BPh4］2 (Ln=La、 Nd、 Sm、 Eu、 Gd、 Tb、 Dy、 Tm)的合成、性质及［Eu(DMSO)7Cl］［BPh4］2的晶体结构

以二甲亚砜(DMSO)作配体与三价希土离子配位,选用四苯硼酸根BPh₄^-作为大阴离子,合成了一系列希土配合物［Ln(DMSO)₇Cl］［BPh₄］₂ (Ln=La、 Nd、 Sm、 Eu、 Gd、 Tb、 Dy、 Tm),并用元素分析,红外光谱对其进行表征,采用单晶X-射线四圆衍射测定了［Eu(DMSO)₇Cl］［BPh₄］₂的晶体     

吡啶-2,5-二羧酸钐(Ⅲ)、镝(Ⅲ)配合物的合成、结构及性质

以Sm(NO₃)₃·6H₂O、Dy(NO₃)₃·6H₂O、吡啶-2,5-二羧酸(H₂pydc)为原料, 用水热合成法合成了2个新的稀土金属配合物[Ln(pydc)₂(H₂O)₅]·4H₂O(Ln=Sm (1), Dy (2)), 单晶结构经X单晶衍射仪分析确定, 两种配合物的晶系均为单斜晶系, C2/c空间群。对晶体的性质进行元素分析、热重、红外光谱, 荧光等分析。结果表明, 配合物1和2在常温下表现出稀土离子相应的特征荧光发射。另外, 本文对两种配合物进行了热稳定性及动力学分析。     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷与镧系硝酸盐、硫氰酸盐配合物的合成表征和CD谱

合成了共15个未见文献报道的三价镧系离子与手性氮杂冠醚(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷(以下以L(+)表示)的配合物Ln(NO₃)₃·L(+)·H₂O(Ln=La、Ce、Pr、Nd); Ln(SCN)₃·L(+)·H₂O(Ln=La、Pr、Nd、Sm、Eu、Gd-Er、Yb)。对所合成配合物进行了元素分析、电导、红外、可见吸收光谱、比旋光度和圆二色谱(CD谱)的测试，并对配合物的有关物理化学性质进行了讨论。     

新颍Mo-Cu-Se簇合物{MoCu3Se3I}(PPh3)3O·0.5CH2Cl2的合成及晶体结构

新颍Mo-Cu-Se簇合物{MoCu₃Se₃I}(PPh₃)₃O·0.5CH₂Cl₂是由［Et₄N］₂MoSe₄、Cu(PPh₃)₂NO₃和KI在乙腈和二氯甲烷1∶1的混合溶剂中反应所得。晶体属单斜晶系，空间群P2_{1相似文献}   

多吡啶配体和银(Ⅰ)三明治配合物的构筑、结构及光谱学分析

三个不同的多吡啶配体:2,3-二(2-吡啶基)喹喔啉(dpq)、2,3,7,8-四(2-吡啶基) 喹喔啉(tppq)和2,3,6,7,10,11-六(2-吡啶基)喹喔啉(hpdq)分别和银反应得到3个银的配合物:[Ag(dpq)(NO₃)₂]_n(1)、[Ag₄(tppq)₂(NO₃)₄](2)和[Ag₆(hpdq)₂(NO₃)₆] (3).结果显示,3个配体分别和银形成了四核(1)、四核(2)以及六核(3)的三明治单晶结构,1和2的四核结构依靠Ag和NO₃^-之间的相互作用进一步延伸为二维面,而3的六核结构依靠C-H…O的氢键作用形成三维网.此外,在研究3个配体和金属银在溶液中的光谱学性质时发现,配体hpdq和银反应的紫外吸收光谱和荧光发射光谱都要比其它2个配体灵敏度高.     

配合物光化学回顾与展望

本文简述了配合物光化学的近期进展和将来趋势.     

COORDINATION COPOLYMERIZATION OF STYRENE WITH MALEIC ANHYDRIDE BY RARE-EARTH COORDINATION CATALYSTS

The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3～NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer c     

COORDINATION CHEMISTRY OF DITHIAZOLYL RADICALS

Reaction of benzo-1,2,3-dithiazolyl, 1, with Pt(PPh₃)₄ has been shown to produce the aminothiolate complex (amt)Pt(PPh₃)₂ [amt = HNC₆H₄S], via oxidative addition of 1 to Pt(PPh₃)₂ followed by S-abstraction by PPh₃. Semi-empirical calculations (AM1 and EHT) have been used to probe the oxidative addition step of this reaction. These studies clearly reveal that close approach of 1 to Pt(PR₃)₂ induces electron transfer from Pt(PR₃)₂ to 1 with concomitant ring opening at the S─N bond and coordination to the metal centre. The SOMO of this complex retains the π* character of the dithiazolyl ring.     

聚合物支载的甘氨酸与Cu^2＋离子的络合性能

本文用N-（3-聚苯乙烯磺酰基-2-羟基丙基）甘氨酸为模型，研究了聚合物支载的氨基酸与Cu2 离子的络合作用性能。树脂与铜离子络合的介质最佳pH值在2～3之间。按照方程：－1n（1－F）=KTt处理求得吸附速率下数K288＝2．47X10－4sec－1。根据Boyd液膜扩散理论，这一吸附过程主要受液膜扩散控制。而且这个反应过程是一种Freundlish吸附过程。G=－30．91KJ／mole和S=129．90J／moleK表明，吸附反应是自发进行的。用斜率法和容量法求得树脂支载的氨基酸基因与铜离子之间的配位比为2:1。     

配位化学的创始与现代化

本文扼要介绍了韦尔纳配位理论的第一篇文章的内容，讨论了配位化学的发展和现代化。配合物稳定性决定于多种作用力与组分间的互补性和拓扑约束性。     

配合物研究的一种最优化方法

本文从配位平衡出发,从光度法对单核、逐级配位配合物的实验研究入手,导出了包含配合物逐级稳定常数为未知数、体系中各物质初始浓度为已知条件的非线性目标函数。对该目标函数用最优化方法求算出配合物的逐级稳定常数的最优估值,利用光度与组分的浓度关系又求得配合物摩尔吸光系数的估计值。采用本手段以平衡移动法研究了5—磺基水杨酸铁(Ⅲ)配位平衡体系的各级稳定常数与摩尔吸光系数,用等摩尔系列法研究了其第一级稳定常数和摩尔吸光系数,取得了满意的结果。     

COORDINATION COMPOUNDS OF LANTHANIDE PERCHLORATES WITH PYRAZINEAMIDE

Abstract

Lanthanide perchlorate complexes of the type [Ln(pyaH)₄] (ClO₄)₃ where Ln=Pr, Nd, Sm, Eu, Tb and Lu, and pyaH is pyrazinamide have been isolated. The compounds were characterized by chemical analyses, molar conductance, vibrational spectra, and electronic absorption and emission spectra. The vibrational spectra and molar conductances indicate that the perchlorate groups are ionic and that pyaH acts a bidentate ligand. The oscillator strengths of the transitions of the Nd(III) complex were determined in terms of the Judd-Ofelt theory. It was possible to use the modified Judd-Ofelt parameters, τλ, for the evaluation of the spectral intensities. In addition, a group-theoretical analysis of the emission spectrum indicates an effective site symmetry D₂ for the Eu(III) complex between 77° K and 10° K.     

COORDINATION COMPOUNDS OF NICKEL WITH TRITHIOCYANURIC ACID

Abstract

Nickel(II) complexes with a combination of trithiocyanuric acid and diamines or triamines of composition [Ni(aepa)(ttcH)(H₂O)], [Ni(dien)(ttcH)(H₂O)], [Ni(dpta)(ttcH)(H₂O)] H₂O, [Ni(phen)₂(ttcH)]H₂O, [Ni(phen)₃](ttcH)-5H₂O and [Ni(1,2-pn)₃](ttcH)-H₂O (aepa = N-(2-aminoethyl)-1,3-propanediamine,dien = diethylenetriamine,dpta = dipropylenetnamine, phen = 1,10-phenanthroline, 1,2-pn = 1,2-diaminopropane. ttcH₃ = trithiocyanuric acid) have been prepared. The compounds have been characterized by means of elemental analysis, IR and electronic spectroscopies and magnetochemical measurements. Selected complexes were studied by thermal analysis. The compounds can be characterized as distorted octahedral Ni(II) complexes. It was found that the trithiocyanuric dianion can act either as a bidentate ligand or be situated out of the coordination sphere of nickel. The crystal and molecular structure of [Ni(dpta)(ttcH)(H₂O)] H₂O was determined. Crystals are monoclinic, space group P2₁/n, with a = 20.316(4), b = 7.967(2), c = 21.401(4) Å, β = 99.23(3)°, K=3419.1(13)ų, Z = 4, T = 293 K. The nickel(II) atom is six-coordinated by three nitrogen atoms from dipropylene-triamine, nitrogen and sulphur from trithiocyanuric acid, and an oxygen atom from a water molecule in a distorted octahedral geometry.     

高压下配合物反应动力学

综述了高压下溶液中化学反应的活化体积△V~≠的定义和测定方法,以及作为配合物取代反应、异构化反应、电子转移反应和光化学反应机理的判据。     

电化学聚合漆酚钐配合物的研究

利用电化学方法合成的聚合漆酚 (EPU)与氯化钐的异丙醇溶液作用 ,得到聚合漆酚钐配合物 (EPU Sm3 + ) .采用红外光谱、紫外 可见光光谱、荧光光谱、XPS光电子能谱、动态机械热分析 (DMTA)以及差热 热重(DTA TG)等手段进行表征 ,确定其每个钐离子与EPU分子中三个链节单元的羟基发生配位 .原子发射光谱(AES)结果确定钐含量达 13 18% .配合物的电阻为 9 6× 10 1 0 Ω(EPU为 7 9× 10 1 0 Ω) .发现因配位作用而使配合物进一步交联 ,而难溶于有机溶剂 ,同时玻璃化转变温度和耐热性能得到提高