共轭多腈配体在功能配合物中的应用

介绍共轭多腈配体的一些特性及其近年来在导电性、磁性、光学性功能配合物的设计与合成中的研究进展。     

功能性多吡啶配体的合成

经过多步反应,合成了10个新的多吡啶配体,其中,有带强吸附性的基团(磷酸基、羧基),有对pH敏感及具有平面大共轭体系的联多吡啶配体及其中间体,用光谱鉴定了它们的结构.     

新型多联吡啶的合成

设计并合成了一种新型配体１，２－二（６”－（６－甲基－４’－苯基－２，２’：６’，２”－三联吡啶基）乙烷，它是由１－（６’－甲基－２’－吡啶基）－３－苯基－２－丙烯－１－酮３与１－（６’－甲基－２’－吡啶基）－羰甲基吡啶碘盐４经改良的Ｋｒｏｈｎｋｅ法先制得取代三联吡啶５，然后在氩气流中，－８０℃与ＬＤＡ，氧化剂１，２－二溴乙烷反应，偶联生成新化合物６。３，４，５，６的结构经元素分析，ＩＲ，ＨＮＭＲ     

大环方酸多齿配体的合成及其光谱特征

合成了一种尚未见文献报道的大环方酸多齿配体，它的结构经ＩＲ、ＵＶ、１ＨＮＭＲ、ＭＳ及元素分析所证实，并考查了它的光谱特征。该化合物的最大吸收波长在７００－８００ｎｍ波长区，它在ＴｉＯ２胶体溶液中，荧光可以被有效淬灭。它与ＴｉＯ２形成的表面复合物的表观复合常数Ｋａｐｐ＝３９０５ｍｏｌ－１．Ｌ。     

多效价树枝状糖苷配体的合成

许多生命过程如细胞间的识别、信号传递等通常依赖于细胞表面的多个配体和受体的协同作用.多效价树枝状糖基配体的合成是研究生物体内蛋白质与糖类、糖类与糖类相互作用的重要途径.本文综述了多效价树枝状糖基配体这类合成配体的最新研究进展,包括以树枝状聚合物、环糊精、糖环、芳烃和大环等为框架的多效价树枝状糖基配体的合成.     

硫化氢荧光探针

简要介绍硫化氢在生命活动中的重要作用。综述了几种新型硫化氢荧光探针的设计与合成,预测了该科研领域的前沿发展趋势。     

异核反夹心配合物[M(AIP)](C5H5)[M'(AIP)](M,M'=V,Cr,Mn)潜在的自旋交叉和价态互变

对反夹心体系[M(AIP)](C₅H₅)[M'(AIP)](M, M'=V, Cr, Mn; AIP=1-氨基-3-亚氨基-1-丙烯脱氢阴离子, C₃N₂ {\mathrm{H}}_5^{-} )进行了理论研究. 结果表明, V-Cr体系存在五重态、 七重态和九重态的多稳态构型; Cr-Mn体系存在三重态、 五重态和七重态的多稳态构型. 在上述体系中, 金属原子的价态会随着异构体自旋态的不同而有所改变, V, Cr和Mn原子均可出现+1和+2价. 由于V-Cr和Cr-Mn体系一些双稳态构型间的自旋交叉能垒较低, 这使自旋交叉和价态互变过程变得可能. 解离能的研究结果表明, V-Cr体系解离能较大, 而Cr-Mn体系解离能略小, 两类体系均较稳定. [M(AIP)](C₅H₅)[M'(AIP)]存在自旋交叉和价态互变的可能性, 并具有较好的解离稳定性, 具有成为分子磁性材料的潜能.     

稀土-异烟酰肼席夫碱配合物的设计、合成与结构（英文）

由异烟酰肼和2-吡啶甲醛合成了席夫碱配体HL,并和稀土离子合成组装得一系列稀土配合物。用X-射线单晶衍射对配合物的结构进行了测定。通过荧光测试发现La配合物有荧光,而Eu,Dy则使配体的荧光淬灭。     

稀土-异烟酰肼席夫碱配合物的设计、合成与结构

由异烟酰肼和2-吡啶甲醛合成了席夫碱配体HL,并和稀土离子合成组装得一系列稀土配合物。用X-射线单晶衍射对配合物的结构进行了测定。通过荧光测试发现La配合物有荧光,而Eu,Dy则使配体的荧光淬灭。     

基于Keggin型金属氧簇与含氮有机配体自组装超分子化合物的晶体结构和电化学研究

通过水热方法合成了超分子化合物(H2bbi)2(SiW12O40).H2O.单晶X射线衍射分析表明化合物结晶于三斜晶系,P-1空间群.化合物中的两种亚单元通过氢键作用形成了超分子结构.此外,循环伏安法研究结果表明了化合物展示3个连续的双电子还原过程.     

混配络合物中配位体最佳浓度比的理论研究

我们认为,如金属离子M能与配位体A和B形成二元络合物,那么在配位数允许和不存在空间障碍的情况下,总有三元络合物形成.但由于两种配位体之间的浓度比例调节不当,会造成三元络合物在溶液里的所有组份中占很小的比例,这样,往往给人们一个错觉,即没有三元络合物形成,三元混配络合物在溶液里所有组份中所占的比例达到极大时,两配位体之间的浓度比例是可以通过计算得到的。     

Interplay and Competition Between Two Different Types of Redox-Active Ligands in Cobalt Complexes: How to Allocate the Electrons?

The field of molecular transition metal complexes with redox-active ligands is dominated by compounds with one or two units of the same redox-active ligand; complexes in which different redox-active ligands are bound to the same metal are uncommon. This work reports the first molecular coordination compounds in which redox-active bisguanidine or urea azine (biguanidine) ligands as well as oxolene ligands are bound to the same cobalt atom. The combination of two different redox-active ligands leads to mono- as well as unprecedented dinuclear cobalt complexes, being multiple (four or six) center redox systems with intriguing electronic structures, all exhibiting radical ligands. By changing the redox potential of the ligands through derivatisation, the electronic structure of the complexes could be altered in a rational way.     

膦配体电子和空间效应对钯催化羰化酯化反应的影响

膦配体修饰的钯催化剂在不饱和化合物羰化酯化反应中使用广泛,其催化活性在很大程度上取决于金属周围的配体环境。膦配体电子和空间效应的调变,可以实现定向催化,甚至可以预测催化行为。新催化反应的开发和现有催化反应的优化都可以通过膦配体的合理设计来实现。配体已经是成为公认的最重要的需要详细研究的变量之一。本文综述了钯催化烯烃羰化酯化反应中,单齿膦配体、双齿膦配体、半稳定膦配体电子和空间效应对活性和选择性的调控作用,并对面临的问题和未来的发展方向进行了探讨,以期对未来设计高效高选择性羰化酯化反应催化体系提供指导。     

含茂、非茂混合配体钛族络合物的合成与催化烯烃聚合的研究进展

目前金属有机钛族络合物的发展呈现出多元化的趋势:茂络合物、非茂络合物以及茂非茂混合配体络合物,而其中茂、非茂混合配体络合物是近年来发展的一个新亮点.关于茂钛族络合物、非茂钛族络合物近年已经有过许多的综述,而关于茂、非茂混合配体钛族络合物的综述却很少.综述了近年来茂、非茂混合配体钛族络合物合成与催化烯烃聚合的研究进展.     

The Preparation of Dicompartmental Multifunctional Group Ligands

A convenient method for the preparation of the phenol-based ligands 1,6-bis(2-thiophenyl)-2,5-bis(2-hydroxy-3-hydroxymethyl-5-methylbenzyl)-2,5-diazahexane and 1,6-bis(5-methyl-2-thiophenyl)-2,5-bis(2-hydroxy-3-hydroxymethyl-5-methyl-benzyl)-2,5-diazahexane possessing two dissimilar compartments having multifunctional groups is reported. To synthesize these ligands, an equivalent of 1,6-bis(2-thiophene)-2,5-diazahexane or 1,6-bis(5-methyl-2-thiophene)-2,5-diazahexane and two equivalents of 2,2-dimethyl-6-methyl-8-(chloromethyl)benzo-1,3-dioxin were reacted in the presence of Na₂CO₃ in 1,4-dioxane, followed by acid hydrolysis of an acetonide-protecting group. Characterization data for the new compounds is reported.     

Copper(I)-2-(2′-pyridyl)benzimidazole catalyzed N-arylation of indoles

CuI-2-(2′-pyridyl)benzimidazole catalyst system can serve efficiently to promote N-arylation of various indoles to afford the N-arylated indoles. The bidentate ligand, 2-(2′-pyridyl)benzimidazole was proved superior to monodentate nitrogen-based ligands and well-known bidentate ligands such as 2,2′-bipyridyl and 1,10-phenanthroline.     

Nitrogen Donor Protection for Atomically Precise Metal Nanoclusters

Surface organic ligands are critical in dictating the structures and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, nitrogen donor ligands have not been used in the protection for well-defined metal nanoclusters until recently. This review focuses on recent developments in atomically precise metal nanoclusters stabilized by different types of nitrogen donor ligands, in which the synthesis, total structure determination and various properties are covered. We hope that this review will provide insights into the rational design of N donor-protected metal nanoclusters in terms of structural and functional modulation.     

MCDOCK: A Monte Carlo simulation approach to the molecular docking problem

Prediction of the binding mode of a ligand (a drug molecule) to its macromolecular receptor, or molecular docking, is an important problem in rational drug design. We have developed a new docking method in which a non-conventional Monte Carlo (MC) simulation technique is employed. A computer program, MCDOCK, was developed to carry out the molecular docking operation automatically. The current version of the MCDOCK program (version 1.0) allows for the full flexibility of ligands in the docking calculations. The scoring function used in MCDOCK is the sum of the interaction energy between the ligand and its receptor, and the conformational energy of the ligand. To validate the MCDOCK method, 19 small ligands, the binding modes of which had been determined experimentally using X-ray diffraction, were docked into their receptor binding sites. To produce statistically significant results, 20 MCDOCK runs were performed for each protein–ligand complex. It was found that a significant percentage of these MCDOCK runs converge to the experimentally observed binding mode. The root-mean-square (rms) of all non-hydrogen atoms of the ligand between the predicted and experimental binding modes ranges from 0.25 to 1.84 Å for these 19 cases. The computational time for each run on an SGI Indigo2/R10000 varies from less than 1 min to 15 min, depending upon the size and the flexibility of the ligands. Thus MCDOCK may be used to predict the precise binding mode of ligands in lead optimization and to discover novel lead compounds through structure-based database searching.     

超分子双膦配体的构筑及应用研究进展

超分子双膦配体是一类新兴起的基于非共价键作用构筑的双膦配体,近年来引起人们的重视.与传统的共价键连接的双膦配体相比,利用非共价相互作用的可逆性和选择性,超分子双膦配体具有合成简便,组合灵活,易于合成超分子配体库,并利用组合化学的方法对催化体系进行优化和筛选等优点.详细综述了近几年发展的基于氢键、配位键、主客体作用和静电作用等弱相互作用的超分子双膦配体,重点讨论了它们的构建方法以及在不对称催化反应中的应用,并对其发展前景进行了展望.     

A general and convenient route to oxazolyl ligands

A diverse range of chiral and achiral oxazolyl ligands, which have many applications including catalysis and luminescent devices, are synthesized simply in three steps from readily available and inexpensive phenol and amino alcohol starting materials. The method can be applied to ligands with electron-donating/-withdrawing and sterically demanding/undemanding substituents, and can conveniently be scaled up to >25 g of product.