μ-氧桥联的双核铜(Ⅱ)配合物Cu2(Salen)2的合成、结构和光谱性质

报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥配位环境中报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥     

酚氧桥联的铜（Ⅰ）—钒（Ⅴ）双核配合物的合成

近年人们对研究桥联多核配合物的兴趣日益增加,已发现许多金属酶的活性部位均为多核配合物和生物体中许多重要的电子转移过程,也涉及到多核桥联结构。基于含酰胺基配体的生物性能,我们用N,N′-乙二水杨酰胶合铜(II)酸根([Cu(samen)]~(2-))作为阴离子双齿配体合成了一系列双核配合物,[Cu(samen)M(L)_x](M=Cu,x=1;M=Ni,Mn,     

两种磺胺类双核铜(Ⅰ)配合物的合成、结构和量子化学研究

分别将磺胺间甲氧嘧啶及磺胺噻唑与一水合乙酸铜(Ⅱ)在水(溶剂)热条件下反应,获得了其相应的金属配合物单晶。用元素分析、红外光谱、紫外光谱和X-射线单晶衍射对其结构进行了表征,结果表明两配合物均为双核化合物,中心Cu原子均采用二配位的直线型几何构型。用密度泛函理论方法对配合物进行了计算,结果表明配合物中金属Cu以+1价存在,这与晶体结构及光谱分析的结果一致,进一步的电荷布局分析结果与晶体结构中的配位情况相符,轨道密度等值面的分析推测配合物具有较好的抑菌活性。     

μ－氧桥联的双核铜（Ⅱ）配合物Cu2(Salen)2的合成、 结构和光谱性质

报道了双核铜(Ⅱ)配合物Cu     

桥联异双核配合物的设计和合成

异双核配合物在生命科学和分子磁性材料研究领域起着重要作用，但它的合成却难度较大。本文介绍四种常用、有效的合成方法。     

双烷氧桥联的双核铜(Ⅱ)Schiff碱配合物的合成及配合行为

通过Salen型双肟配体H₂L¹(H₂L¹=5,5′-二(N,N′-二乙胺)-2,2′-[乙二氧双(氮次甲基)]二酚)与乙酸铜反应,合成了一种双核铜(Ⅱ)配合物[Cu₂(L²)₂](H₂L²=4-(N,N′-二乙胺)水杨醛O-(2-羟乙基)肟),并对其进行了X-射线衍射单晶结构分析。     

双吡唑桥联的大环状钯(Ⅱ)配合物的合成与结构(英)

A dipyrazol-bridged macrocyclic palladium(Ⅱ) complex [{Pd(en)}₄L₄](NO₃)₈ (en=ethylenediamine, L=3,3′,5,5′-tetramethyldipyrazol) 1 was prepared in water through a [4+4] macrocyclization of cis-(ethylenediamine)Pd(Ⅱ) nitrate and the neutral form of the dipyrazol ligand 3,3′,5,5′-tetramethyldipyrazol. This cationic palladium macrocycle is highly distorted rather than a planar macrocycle and can hold eight nitrate anions around the macrocyclic framework through both hydrogen bonding and electrostatic interactions. CCDC: 192017.     

桥联双核铜席夫碱配合物的合成和晶体结构

利用1-苯基-3-甲基-5-吡唑啉酮和水杨酰胺制备了PMP缩水杨酰胺席夫碱及其铜(Ⅱ ) 配合物,根据红外和紫外光谱数据表征了它的结构.利用X射线衍射方法研究了配合物的晶体结构,结果表明配合物为桥联双核铜结构,铜原子为五配位的四方锥构型,每个铜原子与一个配体中吡唑啉酮上的氧原子、席夫碱上的N原子、水杨酰的酚氧原子和溶剂DMF中的氧原子配位,而相邻配体中水杨酰的酚氧原子也参加配位并将两个铜原子连接起来形成桥联双核铜配合物,两个Cu(Ⅱ )原子间的距离为0.3268 nm.芳环堆积作用和分子内及分子间氢键的存在增强了配合物分子的稳定性.     

Synthesis,Crystal Structure and Quantum Chemistry of the Complex [Cu（p-FBA）_2（phen）（H_2O）]

A novel metal-organic complex Cu(p-FBA)2(phen)(H2O) (p-FBA = p-fluorobenzoic acid,phen = 1,10-phenanthroline) has been synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analysis and IR spectra. The crystal belongs to triclinic,space group P1 with a = 7.8043(7),b = 10.4069(9),c = 14.3658(13) ,α = 105.3170(10),β = 96.877(2),γ = 96.7580(10)o,V = 1103.56(17) 3,Mr = 539.96,Z = 2,Dc = 1.625 g/cm3,μ = 1.050 mm-1,F(000) = 550,the final R = 0.0324 and wR = 0.0952. In the crystal,the structure consists of discrete molecules containing a five-coordinate copper(Ⅱ ) in a distorted square pyramidal configuration. Intramolecular O-H···O hydrogen bonds,weak intermolecular C-H···O hydrogen bonds and π-π stacking link the molecules into a one-dimensional chain structure. The study on the title complex has been performed with quantum chemistry calculation by means of G03W package on the Lanl2dz basis set. The stabilities of the complex together with the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated.     

以甲氧基苯甲酸为配体的两个双核铜配合物的合成、晶体结构和理论计算

以2-甲氧基苯甲酸(HL1)、2,3-二甲氧基苯甲酸(HL2)及甲醇为配体,合成了配合物Cu2(L1)4(CH3OH)2(1)和Cu2(L2)4(CH3OH)2(2),并通过红外、元素分析、X-射线粉末和单晶衍射等研究手段表征了其结构。配合物1属单斜晶系,空间群P21/n;配合物2属三斜晶系,空间群P1。2个配合物都具有双核铜结构,由2个铜离子、4个L配体分子和2个甲醇配体分子组成,其中配体L通过双齿配位模式与铜离子配合。研究了2个配合物的热稳定性,并通过Gaussian 09软件密度泛函理论B3LYP方法进行了理论研究。     

以甲氧基苯甲酸为配体的两个双核铜配合物的合成、晶体结构和理论计算

以2-甲氧基苯甲酸(HL₁)、2,3-二甲氧基苯甲酸(HL₂)及甲醇为配体,合成了配合物Cu₂(L₁)₄(CH₃OH)₂ (1)和Cu₂(L₂)₄(CH₃OH)₂ (2),并通过红外、元素分析、X-射线粉末和单晶衍射等研究手段表征了其结构.配合物1属单斜晶系,空间群P2₁/n;配合物2属三斜晶系,空间群P1.2个配合物都具有双核铜结构,由2个铜离子、4个L配体分子和2个甲醇配体分子组成,其中配体L通过双齿配位模式与铜离子配合.研究了2个配合物的热稳定性,并通过Gaussian 09软件密度泛函理论B3LYP方法进行了理论研究.     

Copper(II) complexes of tridentate SNO ligands: synthesis,characterization and crystal structure

A new series of binary copper(II) complexes, [Cu(L)₂] (2) [where L is a monobasic tridentate methylthioazophenolate having NSO donor sets], has been synthesized. The reddish brown colored complexes have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The detailed structure analysis of one of the complexes, [Cu(1a)₂] (2a), by single-crystal X-ray crystallography shows that thioether-S donor center participates in coordination with the copper(II) ion with a weak interaction with long Cu–S(thioether) bond distances [2.956(2) Å and 2.925(2) Å]. Electrochemical study of the complexes in methanol using TBAP as supporting electrolyte shows that heterogeneous electron-transfer rate is low at the applied potential.     

Syntheses, crystal structures and properties of Co(II) complexes with N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine (bpb), and Cd(II), Hg(II) complexes with reduced bpb

Five novel coordination polymers, [Co(bpb)₂Cl₂] (1), [Co(bpb)₂(SCN)₂] (2), [Cd(H₄bpb)_0.5(dmf)(NO₃)₂] (3), [Cd₂(H₄bpb)Br₄] (4), and [Hg₂(H₄bpb)I₄] (5) [bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine, H₄bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethylamine], were synthesized and their structures were determined by X-ray crystallography. In the solid state, complex 1 is a 1D hinged chain, while 2 has 2D network structure with the ligand bpb serving as a bridging ligand using its two pyridyl N atoms. The imine N atoms keep free of coordination and bpb acts as a bidentate ligand in both 1 and 2. Complexes 3, 4, and 5 with reduced bpb ligand, i.e. H₄bpb, show similar 2D network structure, in which ligand H₄bpb serves as a tetradentate ligand. Thermogravimetric analyses for complexes 1-5 were carried out and found that they have high thermal stability. The magnetic susceptibilities of compounds 1, 2 were measured over a temperature range of 75-300 K.     

Synthesis and Characterization of Nickel(II) and Copper(II) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082(2), b = 15.447(3), c = 18.784(4) , V = 3505.7(12) 3, Mr = 731.50, Dc = 1.386 g/cm3, μ = 0.606 mm–1, F(000) = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I > 2σ(I). For 2, a = 12.181(2), b = 15.501(3), c = 18.877(4) , V = 3564.3(12) 3, Mr = 736.33, Dc = 1.372 g/cm3, μ = 0.665 mm–1, F(000) = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π···π interactions.     

Thermodynamic Studies on the Complexation Reactions of Copper(II) Complex of o2n2-Donor Macrocycle with Halide and Pseudohalide Ions

Complexation reactions of 5,6,7,8,9,10,16,17-octahydrodibenzo[e, m][1, 4]dioxa-[8, 11]diazacyclotetradecine-copper(II) complex with halide and pseudohalide ions have been studied at 25.0° in three water-methanol mixed solvents by spectro-photometric method. It is found that the equilibrium constants increases in the order of 50 vol.% CH₃OH<75 vol.% CH₃OH<95 vol.% CH₃OH for solvents and I-<Br^?<CI^?<SCN^?, N^?₃ for anions.