配位化学近期进展

经历了五十年代复兴时期以后,无机化学与有机化学、物理化学、生物化学、固体化学等学科的相互渗透和交叉,形成了近代配位化学。它的发展对元素分离提取技术的进一步改进,新颖催化反应及高效高选择性催化剂的发现,     

配位场稳定化能的计算及其应用实例

配位场理论在解释配合物的热力学,立体化学以及动力学等性质时都要用到配位场稳定化能(LFSE)的概念。前人的文献只研究了正八面体,正四面体或者个别低对称性配合物的配位场稳定化能。如果要系统地研究配合物的构型优先化,推断配合物取代反应的历程,只有上述特殊构型配合物的配位场稳定化能是不够的。为此本文计算了二十三种常见构型配合物的d~1-d~(10)体系的配位场稳定化能。     

壳聚糖镍和壳聚糖镧配位聚合物的配位数研究

从ＩＲ、ＥＳＲ和ＸＰＳ的测试结果可知,Ｎｉ＾２＋或Ｌａ＾３＋与壳聚糖（ＣＳ）键节单元上的氨基Ｎ和仲羟基Ｏ发生配位反应,形成ＣＳ－Ｎｉ＾２＋或ＣＳ－Ｌａ＾３＋配位聚合物膜。通过电导率研究其配位数,发现Ｎｉ＾２＋或Ｌａ＾３＋可与壳聚糖的３个或５个键节单元配位。根据以上的实验可推定中心离子Ｎｉ＾２＋与壳聚糖３个键节单元上的氨基Ｎ和仲羟基Ｏ结合,形成六配位的ＣＳ－Ｎｉ配位聚合物Ｌａ＾３＋与壳聚糖５个键节单     

我国配位化学进展

简述了我国配位化学的发展、进展和特点。     

^1^5N标记邻位芳香羟肟配位体的核磁共振研究

利用稳定同位素的磁性和质量同位素效应已成为研究有机结构化学的重要手段。我们为研究部位芳香及其芝渡金属如Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Fe(Ⅱ)配合物的光     

配位化合物教学研究

在讲授配位化合物一章时,可以利用之前学过的物质结构理论和化学平衡的原理,让学生更好地理解和掌握配合物的价键理论和配位平衡的知识;同时,可以对大学化学所学的主要知识进行总结,做到温故知新,融会贯通,从而对大学化学的学习做一个整体的总结和提高。     

配位化学的发展史

自从1893年瑞士化学家维尔纳创立配位化学已来,配位化学理论得到不断发展,逐渐完善。经过化学家们100多年的努力,由传统经典的配合物,发展到今天的配位超分子化合物,并显示出结构和功能上的优越特性,成为现代无机化学的一个发展方向。     

配位化学的发展史安徽省教育厅人文社科

自从1893年瑞士化学家维尔纳创立配位化学已来,配位化学理论得到不断发展,逐渐完善.经过化学家们100多年的努力,由传统经典的配合物,发展到今天的配位超分子化合物,并显示出结构和功能上的优越特性,成为现代无机化学的一个发展方向.     

壳寡糖与硝酸钕配合物的合成和配位机理研究

用壳寡糖与硝酸钕反应,制备了壳寡糖-钕配合物。用红外光谱和X射线光电子能谱等分析测试手段对配合物进行了表征。从IR和XPS的测试结果可知,Nd^3＋与壳寡糖上的氨基N和仲羟基O配位,形成壳寡糖-钕配位聚合物。通过电导率研究其配位数,发现Nd^3＋可与壳寡糖的4个链节单元配位.根据以上的实验可推定中心离子Nd^3＋与壳寡糖4个链节单元上的氨基N和仲羟基O结合,形成八配位的壳寡糖-钕配位聚合物。     

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 Coordination Number – an “Inorganic Chameleon”

The purpose of the present article is to describe the changing ambiguous character of the term “coordination number” and its present-day definition in structural chemistry, particularly of typical solids (assemblies of particles with short-range and long-range order). An effort is made at the same time to describe the crystal structure of solids as simply as possible while also taking long-range order into account, i.e. by determining “effective” coordination numbers by the geometrical “polyhedron method” or from MAPLE (Madelung Part of Lattice Energy) values.     

Synthesis of strapped zinc chlorophyll derivatives and their complexation with a single axial ligand

Zinc chlorins having a bridged moiety between 3- or 8- and 17-positions were designed as protected chlorophylls at one of π-faces, aiming at the investigation of asymmetric coordination ability towards the central metal. These strapped chlorins were synthesized by the cyclization of the dihydroxylated chlorins with dicarboxylic acid dichlorides under highly diluted conditions. The synthetic zinc chlorins complexed with pyridine as an axial ligand in benzene to form 5-coordinated species. The 1:1 binding constants determined by UV-vis titration method were smaller than those of the corresponding acyclic (unstrapped) compounds.     

不同含羧酸纤维与铁离子的配位反应动力学及配合物的催化降解性能

分别使用具有相似羧基含量的海藻纤维、 丙烯酸接枝改性聚四氟乙烯纤维和聚丙烯纤维(PAA-g-PP 和PAA-g-PTFE)3种含羧酸纤维与Fe³⁺进行配位反应, 研究和比较了反应的动力学特性及影响因素. 将3种含羧酸纤维铁配合物分别作为非均相Fenton反应催化剂应用于染料降解反应中, 分析和评价了其配位结构和表面性能对催化活性的影响. 结果表明, 在所涉及的温度和浓度范围内, 3种含羧酸纤维与Fe³⁺的反应均很好地符合Langmuir等温吸附模型和Lagergren准二级动力学方程. Fe³⁺初始浓度的增加会降低反应速率常数, 而反应温度的升高则会增加配合物中Fe³⁺的配合量. 在相同反应条件下, 海藻纤维比PAA-g-PP和PAA-g-PTFE更容易与Fe³⁺发生反应, 且反应速率常数和Fe³⁺配合量按照下列顺序排列: 海藻纤维>PAA-g-PP>PAA-g-PTFE. 3种含羧酸纤维铁配合物都能够在染料氧化降解反应中作为非均相Fenton催化剂, 且紫外光比可见光更能够提高其催化活性. 海藻纤维铁配合物比其它2种含羧酸纤维铁配合物具有更好的催化作用, 这与三者在配位结构和表面性能之间的显著差异有关.     

电化学聚合漆酚钴膜配位结构与催化性能研究

电化学方法合成的聚合漆酚 (EPU)通过与氯化钴的异丙醇溶液作用 ,生成聚合漆酚钴配合物膜(EPU Co3+ ) .采用红外光谱、XPS光电子能谱、DTA TG、动态机械热分析 (DMTA)以及原子发射光谱 (AES)等手段进行表征 ,确定其配位结构 ,即每个钴离子与EPU中两个链节单元的羟基发生配位而交联 ,因此玻璃化转变温度和耐热性能均得到提高 .实验表明 ,此配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发VAc的聚合     

From a 1D Sb Coordination Polymer to a 3D Sb Framework with Pyrazine: Switching off the Stereochemically Active Lone-Pair

The one-dimensional coordination polymer ¹_∞[SbCl₃(pyz)] ( 1 ) and the three-dimensional frameworks ³_∞[Sb₂Cl₆(pyz)₃] ( 2 ) and ³_∞[Sb₂I₆(pyz)₃] ( 3 ) were obtained from SbX₃ (X: Cl, I) and pyrazine (pyz). These coordination polymers are, to the best of our knowledge, among the first Sb-based coordination polymers constructed from antimony halides and N-donor ligands. While the Sb³⁺-cations in 1 are coordinated in a square-pyramidal coordination sphere indicating a stereochemically active lone-pair, no stereochemically active Sb-lone-pair is present in 2 and 3 having octahedral coordination spheres around Sb^III. Since 2 can be obtained by heating of 1 , the character of the Sb-lone-pair in 1 can be changed by thermal treatment. Thereby the interlinkage is increased via an additional pyrazine molecule resulting in the octahedral coordination in 2 .     

Influence of the Different Dicarboxylate Ligands on The Topological Net of Manganese(II) Coordination Polymers: Syntheses,Crystal Structures. and Luminescent Properties

The self‐assembly of Mn^II ions and 1,4‐bis(2‐methyl‐imidazole‐1‐yl)benzene (bip) with two different dicarboxylate ligands, benzophenone‐4,4′‐dicarboxylic acid (H₂bda) and 1,4‐naphthalenedicarboxylic acid (H₂nda) via hydrothermal synthesis resulted in two interesting coordination polymers, [Mn(bda)(bip)]_n ( 1 ) and [(Mn(nda)(bip)_0.5(H₂O)]_n ( 2 ). Their structures were determined by single‐crystal X‐ray diffraction and elemental analyses, as well as IR spectroscopy. Complex 1 exhibits an unusual polycatenated 2D+2D→3D framework. Complex 2 shows a twofold interpenetrated pcu net. In addition, the solid‐state photoluminescent properties of 1 and 2 were investigated at room temperature.     

The Crystal Chemistry of Copper Oxometalates

Up to three or four years ago oxocuprates were a class of chemical compounds no more remarkable than countless others. Then, as a result of the euphoria surrounding the high-temperature oxide superconductors and the discovery that copper plays an essential role in these materials, there was a world-wide awakening of interest in copper-containing oxide compounds. The number of scientists engaged in the synthesis and structure determination of copper oxometalates has grown from just a few to very many. As superconductivity is inseparably connected with the structure of the solid state, there has been a spontaneous awakening of interest in the role of copper in the crystal chemistry of solid materials, leading to new research projects on this aspect of oxocuprates. Most of the work published so far on the interesting chemistry of this group of compounds has related to individual compounds. New aids in describing complex solid state structures are now available through the development of methods that give three-dimensional displays of crystal structures using computer graphics terminals, as this review illustrates for the example of the oxocuprates.     

Application value of a new Co(II) complex in treatment of glioma by inducing glioma cell apoptosis

When a 3,5-bis(3,5-dicarboxylphenoxy)benzoic acid (H₅L) ligand reacted with Co(II) salt as well as the 4′-bis(benzoimidazo-1-ly)biphenyl) (4,4′-bbibp) ligand, a novel coordination polymer based on Co with the chemical composition of {[Co₂(HL) (4,4′-bbibp)₂]·4(H₂O)}_n has been created. The single crystal X-ray diffraction and elemental analysis of compound 1 were carried out and the data were recorded. Its application value on the glioma was evaluated with the CCK-8 assay and the Annexin V-FITC/PI apoptosis assay. It has been shown that carboxyl groups in Co complexes can form multiple binding interactions with target proteins, however, the imidazole group doesn't form any binding interaction.     

Supramolecular Influences on Metal Ion Coordination: Lead(II) under Eight-coordination

Crystal structure determinations on the “acid salt” of Pb(II) and dipicolinic acid (pyridine-2,6-dicarboxylic acid, dipicH²), regarded as composed of dimer entities, [Pb²(dipic)²(dipicH²)²(OH²)⁶], 1, infinitely cross-linked, and on the complex of 2,4-dinitrophenol (2,4-DNPH), a simpler coordination polymer, [Pb(2,4-DNP)²]n, 2, show both solid state structures to be influenced by π-stacking of the ligands. Although the Pb(II) coordination environment in 1 can be regarded as “hemidirected” and that in 2 as “holodirected”, it is argued that inter-dimer stacking interactions, rather than lone pair effects, are responsible for the distorted 9-coordination of Pb in 1. In 2, Pb adopts close-to-cubic 8-coordination.