大环双核Zn(Ⅱ)配合物的合成与结构表征

在Zn²⁺的存在下,2,6-二甲酰基对氟苯酚和1,4-丁二胺通过环缩合反应,合成了一种对称的大环双核锌配合物：[Zn₂L¹(μ-OAc)]ClO₄·0.5CH₃OH。通过远红外、紫外、二维核磁、电喷雾质谱和荧光等研究了配合物的结构。并用X-射线晶体衍射测定了配合物的结构。晶体结构表明,在一个不对称的单元中含2个化学组成相同、分子结构基本相似的大环配合物阳离子A和B。每个大环中的锌离子都处于扭曲的四面体中,且由2个酚氧桥相连。配合物的三维结构由配合物中的非经典氢键构成。     

席夫碱大环双核锌配合物的合成与表征

本文用丙酮和乙二胺在高氯酸催化下合成了四氮杂十四环席夫碱(1),并用此化合物(1)与氧化锌和叠氮化钠反应,生成锌的双核大环配合物。通过X-射线单晶衍射和红外光谱对其进行了结构表征。该配合物属单斜晶系,C2/c空间群,晶胞参数为a=2.4914(2)nm,b=1.4 9748(13)nm,c=1.26800(11)nm;β=102.1900(10)°;v=4.6240(7)nm3,Z=4,Dc=1.482Mg/m3,Mr=1032.03,F(000)=2160,最终R=0.0506,wR=0.1434。该配合物中锌原子是五配位,它们分别和大环配体上的4个氮原子及叠氮根负离子两端的氮原子配位形成畸变的三角双锥构型。     

具有两种不同配位隔室的含酚桥基''N~5O~2'' Schiff碱大环铜钠 异双核配合物的 合成及结构

以Cu~(2+)和Na~+同时作为模板,用2,6-二甲酰基对甲苯酚直接与一定比例的乙二胺,二-1,2-亚乙基-三胺发生[2+2]型 Schiff碱缩合,合成了含两个不同隔室Schiff碱大环配体(L~2-)的铜钠异双核配合物[CuNaL(ClO_4)].并对它进行了元素分析,UV-Vis,IR,1H NMR,摩尔电导和ESR谱等项表征.ESR谱显示三个g值峰,对应的gx,gy,gz值分别为1.987,2.168,2.233.单晶X射线四圆衍射分析表明,该配合物为单斜晶系,空间群P2_1/n,晶胞参数a=0.9255(3)b=1.7689(2),c=1.6055(2)nm,β=101.69(2)°,Z=4,V=2.574nm.Cu原子和Na原子分别位于大环配体V~2-的‘N_2O_2’四配位和‘N_3O_2’五配位隔室.Cu~(2+)的配位数为4,基本保持平面构型、Cu—O和Cu—N平均键长分别为0.1911,0.1926nm,Na~+除与L~2-配位外,还与单齿高氯酸根结合,配位数为6.Na——O和Na——N的平均键长分别为0.2379,0.2468nm.Cu…Na间距离为0.3227nm.     

一种大环化合物的晶体结构及其双核铜配合物的酪氨酸酶活性研究

A ring-contracted form macrocycle, 29,30-dioxo-3,6,9,17,20,23,29,30-octaazapentacyclo[23,3,1,1^11,15,0^2,6,0^16,20]-triacontaneocta- 1 (28),9,11 (12), 13,15(30),23,25(29),26-ene (L) was synthesized by condensation of diethyltriamine with pyridine-1-oxide-2,6-dicarboxaldehyde. A porous three-dimensional layer structure in its crystal was formed by self-assembly through hydrogen bonds and π-π interaction. Its dinuclear copper(I) complex [Cu2L(MeOH)2]-(BF4)2*2H2O and dinuclear-copper(II) complex [Cu2L(MeOH)2](ClO4)4*2H2O were obtained and could oxidize catalytically four phenolic substrates hydroquinone, 2-methyl-hydroquinone, 2,6-di-tert-butylphenol and 2,6-dimethylphenol, in a mixture of methanol and acetonitrile (V : V, 4 : 1). The copper(I) complex reacted with dioxygen to form an oxygenated species as an initial active intermediate for oxidation of the phenols. Oxidation of the substrates by the copper(II) complex produced a copper(I) complex and the oxidation products of the substrates.     

新型双核铜配合物的结构及DNA切割活性

合成了一种以吡啶-2,6-二甲酸(dipicH2)桥联的新型双核邻菲咯啉铜配合物，[Cu₂(phen)₃(dipic)(OH)]·Na·ClO₄·2H₂O(phen 为1，10-菲咯啉的缩写)。该配合物晶体属于单斜晶系，P2₁/n空间群，a=1.225 85(2) nm，b=2.196 3(3) nm，c=1.619 5(2) nm，β=100.951(2)°。配合物分子中的两个中心铜离子均处于变形的四方锥配位环境，并通过吡啶-2，6-二甲酸配体上的氧氮原子相连。凝胶电泳结果表明，在pH 7.4，温度37 ℃，以抗坏血酸为还原剂或在H₂O₂的存在下，该配合物对超螺旋pBR322 DNA表现出显著的切割活性，为人工金属核酸酶的研究提供了新的例证。     

双核大环配合物及其仿生物性

双核大环配合物在模拟金属蛋白活化中心，键合活化小分子及作为双功能催化剂方面具有广阔应用前景。本文就西夫碱型，串连型，具有“软”“硬”空腔的单大环，双大环及大多环双核配合及其配合物的性质和它们仿生方面的研究进展进行综述报道。     

不对称大环双核铜配合物的合成,性质及抗菌活性

以配体N,N′-二甲基-N,N′-二(3-甲酰基-5-氯水杨醛)乙二胺(H_2L)与乙二胺、醋酸铜、高氯酸铜通过模板反应缩合制备了新的不对称大环双核铜配合物[Cu_2(L)(ClO_4)·H_2O]·ClO_4,通过元素分析、红外光谱、电喷雾质谱、X-晶体衍射对配合物进行结构表征,表明不对称大环配合物中的一个铜(Ⅱ)离子与大环中两个胺的氮原子、两个酚羟基的氧原子以及高氯酸根中的氧原子形成5配位,另一个铜(Ⅱ)离子与大环中的两个亚胺氮原子、两个酚羟基氧原子以及配位的水分子中的氧原子形成5配位;电化学性质研究表明铜(Ⅱ)离子的电极过程是一个不可逆单电子传递过程,磁性研究表明配合物的铜(Ⅱ)离子之间存在反铁磁性偶合,抗菌实验测试了配体和双核铜(Ⅱ)配合物对金黄色葡萄球菌、绿脓杆菌、大肠杆菌的抗菌活性,结果表明:在质量浓度为2.0g·L~(-1)时,配体和双核铜(Ⅱ)配合物的抗菌活性最强。     

含双二苯基膦甲烷双核铜Ⅰ配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷 (dppm)的双铜 配合物 [Cu2 (dppm) 2 L2 ](NO3) 2 (配体L分别是 2 ,2’ 联吡啶 (1)、邻菲咯啉 (2 )、2 ,9 二甲基 邻菲咯啉 (3)、吡啶 (4 ) ],并经核磁、热分析、光电子能谱等方法表征了配合物的性质。配合物 (1)的晶体结构显示 ,dppm作为桥式双齿配体、联吡啶作为双齿配体分别与铜原子形成四面体配位结构 ,硝酸根离子位于配合物外界     

双环八氮杂大环双核铜配合物催化羧酸酯水解研究

合成了一类新的双环二氧大环四胺双核铜配合物，其组成经元素分析、热重/差热分析、摩尔比法及等物质的量连续变化法所确证。在水溶液中，详细研究了其催化2-吡啶甲酸对硝基苯酚酯(PNPP)水解的动力学和机理，并与相应的单核铜配合物进行了对比。结果表明，此双核铜配合物能有效地催化PNPP的水解；两个金属中心之间具有明显的协同作用，较好的模拟了某些天然水解金属酶的“双功能催化机理”。     

含双二苯基膦甲烷双核铜(I)配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷(dppm)的双铜(Ⅰ)配合物[Cu2(dppm)2L2](NO3)2(配体L分别是2,2'-联吡啶(1)、邻菲咯啉(2)、2,9-二甲基-邻菲咯啉(3)、吡啶(4)],并经核磁、热分析、光电子能谱等方法表征了配合物的性质.配合物(1)的晶体结构显示,dppm作为桥式双齿配体、联吡啶作为双齿配体分别与铜原子形成四面体配位结构,硝酸根离子位于配合物外界.     

大环多胺配体BDBPH的设计合成及其晶体结构

用Pb(SN)₂作模板,2,6-二甲酰基对甲苯酚与二亚乙基三胺通过[2+2]缩合反应,经NaBH₄还原、脱Pb²⁺、酸化等操作,得晶体BDBPH·6HBr·4H₂O.晶体属单斜晶系,P2_1/c空间群,晶体学参数:a=1.4441(5)nm,b=1.1482(4)nm,c=1.2090(6)nm,α=90°,β=96.92°,γ=90°,V=1.9900nm³大环分子采取椅式构型,6个Br-和4个H₂O分子对称分布于大环两侧.该大环配体结构新颖,可用于多种金属配合物的研究,对进一步了解金属酶活性中心的结构及其催化作用机理具有重要价值.     

Synthesis and Characterization of Metal Complexes of two Novel Pyridine‐Derived Macrocyclic Ligands Bearing o‐ and p‐Nitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the two secondary aminic groups of the oxaazamacrocyclic precursor L with o‐nitrobenzylbromide (L¹) or p‐nitrobenzylbromide (L²). Metal complexes of L¹ and L² have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, ¹H and ¹³C NMR spectroscopy and magnetic studies. Crystal structures of ligands L¹ and L², as well as complexes [CdL¹(NO₃)₂]·2CH₃CN and [Ag₂Br(L²)₂](ClO₄)·2CH₃CN have been determined by single crystal X‐ray crystallography.     

含双水杨醛Schiff碱配体的双核配合物的合成及晶体结构

合成了4个含双水杨醛Schiff碱配体的双核过渡金属配合物,并通过元素分析、红外光谱、紫外光谱,热重分析以及X-射线单晶衍射等手段对所得配合物进行了表征。结果表明,配合物1、3和4都属于三斜晶系,空间群为P1,而配合物2属于单斜晶系,空间群为C2/c。在配合物1中,2个Cu髤离子具有不同的配位构型,其中一个Cu髤形成了五配位的四角锥构型,而另一个Cu髤形成了平面正方形构型。配合物4中,通过酚氧原子的桥联作用,双核单元相互连接形成了一维链状结构。     

Metal Complexes with a New Tetrapyridyl Pendant Armed Macrocyclic Ligand. X‐ray Crystal Structures of CuII and NiII Complexes

A new pendant‐armed macrocyclic ligand, L¹, bearing four pyridyl pendant groups has been synthesized by N‐alkylation of the tetraazamacrocyclic precursor L with 2‐picolyl chloride hydrochloride. Metal complexes of L¹ have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, ¹H and ¹³C NMR spectroscopy and magnetic studies. Crystal structures of the ligand L¹ as well as of the complexes [Ni₂L¹](ClO₄)₄·5CH₃CN and [Cu₂L¹](ClO₄)₄·4.5CH₃CN have been determined by single crystal X‐ray crystallography. The X ray studies show the presence of two metal atoms within the macrocyclic ligand in both metal complexes showing five coordination arrangement for the metal ions.     

Structural Relationships between the Hemiporphyrazine Macrocyclic Ligand and its Metal Complexes. II.: Planar Neutral Ligand,C26H16N8, and Four Isomorphous Metal Complexes, [M(C26H16N8)(H2O)], M=Mn(II), Co(II), Cu(II), Zn(II)

Crystal and molecular structures of the planar neutral ligand, C₂₆H₁₆N₈, and the four isomorphous five-coordinated metal complexes, [M(C₂₆H₁₆N₈)(H₂O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH₂, C₂₆H₁₆N₈, belongs to the P 2₁/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H₂O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 ų. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH₂·H₂O) and the nickel complex [Nihp]⁵. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H₂O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.     

基于3,4-吡唑二甲酸为配体的两个过渡金属配合物的合成、结构及荧光性质

以3,4-吡唑二甲酸(H3pdc)为配体分别与氯化铜、氯化镍反应,得到了2个过渡金属配合物:[M(H2pdc)2(H2O)2]·2H2O(M=Cu(1)和Ni(2)),用元素分析、红外光谱、X-单晶衍射结构分析、热重分析和荧光分析对其进行了表征。晶体结构分析表明配合物1和2均为单核结构,金属离子与来自2个H2pdc-中的2个N原子和2个羧基O原子,以及2个水分子中的2个O原子配位,形成六配位的八面体构型。配合物1和2中的独立结构单元[M(H2pdc)2(H2O)2]·2H2O通过3种分子间氢键(O-H…O,N-H…O和C-H…O)形成三维(3D)空间结构;此外我们还研究了配合物1和2的热稳定性和荧光性质。     

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu(C9H11N3)Cl2]2 (C18H22Cl4Cu2N6), has been synthe- sized and characterized by X-ray structure determination. It crystallizes in the triclinic P1 space group with a = 7.526(3), b = 9.473(4), c = 9.535(3) , α = 117.214(10), β = 108.251(9), γ = 91.560(6)o, V = 562.3(4) 3, Z = 1, Mr = 591.30, F(000) = 298, Dc = 1.746 g/cm3, μ(MoKα) = 2.385 mm-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted trigonal bipyramid of five coordination atoms (two nitrogen and three chlorine atoms). Two copper(II) atoms were bridged by two chlorine anions (Cl(2) and Cl(2a)) to form a Cu(II)-Cu(II) binuclear entity with the distance between two copper(II) atoms of 3.398 .     

Studies on PNPP Hydrolysis Catalyzed by Divalent Metal Ion Macrocyclic Schiff Base Complexes in Micellar Solution

Two transitional metal ion macrocyclic Schiff base complexes, NiL and CuL were synthesized and characterized, and the metallomicelles made up of the nickel(II) and copper(II) complexes and surfactants(LSS, Brij35, CTAB), as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester (PNPP). The analysis of specific absorption spectrums of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Ni(II) or Cu(II) complexes, have formed in the reaction processes of the PNPP catalytic hydrolysis. In this, based on the analytic result of specific absorption spectrum, the mechanism of PNPP catalytic hydrolysis has been proposed; a kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis has been established on the foundation of the mechanism proposed; the acid effect of reaction system, structure effect of the complexes, effect of temperature and effects of micelle on the rate of PNPP hydrolysis catalyzed by the complexes also have been discussed.     

Structure and Magnetism of two Polynuclear Complexes Containing both Macrocyclic and Azido Ligands

The two complexes of formula [Cu₂(CuL)₂(μ‐N₃)₄] · 2CH₃OH ( 1 ) and [Cu₂(NiL)₂(μ‐N₃)₄] · 2CH₃OH ( 2 ) (CuL and NiL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien), were synthesized and structurally determined. The magnetic susceptibility data of 1 and 2 were analyzed. For complex 1 , magnetic measurements show alternating ferromagnetic and antiferromagnetic exchange couplings J₁ = 23.67 cm^–1, J₂ = –189.11 cm^–1, zJ’ = –0.62 cm^–1. For complex 2 , the doubly bridged asymmetric EO promotes a ferromagnetic interaction between Cu^II and Cu^II ions(J = 40.764 cm^–1).