SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF DIMERIC Co(II) AND Ni(II) COMPLEXES CONTAINIGN N,N'-(PHENYL-2-PYRIDINYLMETHYLENE)-3,3',5,5'-TETRAMETHYLBENZIDINE

The N,N'-(phenyl-2-pyridinylmethylene)-3,3',5,5'-tetramethylbenzidine and its dimeric Co(II) and Ni(II) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while the bimetal complexes were determined by elemental analyses,IR spectra as well as the single-crystal X-ray diffraction.The nickel complex showed high activity for ethylene polymerization and its cobalt analogue showed negligible active in ethylene activation.     

SYNTHESIS,CHARACTERIZATION AND CATALYTIC BEHAVIOR OF DIMERIC Co(Ⅱ) AND Ni(Ⅱ) COMPLEXES CONTAINING N,N -(PHENYL-2-PYRIDINYLMETHYLENE)-3,3 ,5,5 -TETRAMETHYLBENZIDINE

The N,N'-(phenyl-2-pyridinylmethylene)-3,3',5,5'-tetramethylbenzidine and its dimeric Co(Ⅱ)and Ni(Ⅱ) complexes were synthesized.The organic compound was characterized by elemental analyses,IR and NMR spectra,while the bimetal complexes were determined by elemental analyses,IR spectra as well as the single-crystal X-ray diffraction.The nickel complex showed high activity for ethylene polymerization and its cobalt analogue showed negligible active in ethylene activation.     

Synthesis and Characterization of 2,6-Bis(imino)phenoxy Cobalt Complexes

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3d过渡金属的2-羰基丙酸(4-吡啶甲酰基)腙配合物的合成, 表征及导电性质研究

本文制备了2-羰基丙酸(4-吡啶甲酸基)腙(H2PPFH)的六种过渡金属配合物和Mn(II)配合物的单晶。通过元素分析, 红外和紫外光谱, 差热和热重分析对各配合物的结构和性质进行了表征。配合物的通式为M(PPFH).n[H2O(II)=Mn, Fe, Co,Ni, Cu, Zn, n=0～2]。并通过X射线单晶衍射仪对Mn(II)配合物的晶体结构进行了测定。分析表明该晶体属单斜晶系。空间群为P21/n, Z=4, a=1.1252, b=0.9828,c=1.3708nm, β=66.03°, R=0.28。通过配合物的导电性能的测试, 发现它们都具有半导电性质。     

Homoleptic Zinc(II) Complexes Based on 4′‐(2‐Thienyl)‐terpyridine: Preparation,Structures, and Properties

The homoleptic complexes Zn^II(4′‐(2‐(5‐R‐thienyl))‐terpyridine)₂(ClO₄)₂ [R = hydrogen ( 1 ), bromo ( 2 ), methyl ( 3 ), and methoxy ( 4 )] were prepared. Their structures were determined by single‐crystal X‐ray diffraction analyses, and further characterized by high resolution mass, infrared spectra (IR), and elemental analyses. Single crystal X‐ray diffraction analysis showed that Zn^II ions in the complexes are both six‐coordinate with N₆ coordination sphere, displaying distorted octahedral arrangements. The absorption and emission spectra of the homoleptic Zn^II complexes were investigated and compared to those of the parent complex Zn^II(4′‐(2‐thienyl))‐terpyridine)₂(ClO₄)₂. The UV/Vis absorption spectra showed that the complexes all exhibit strong absorption component in UV region, moreover, complex 4 has an absorption component in the visible region. Thus, the photocatalytic activities of the complexes in degradation of organic dyes were investigated under UV and visible irradiation.     

Synthesis, characterization and antioxidant activity of naringenin Schiff base and its Cu(II), Ni(II), Zn(II) complexes

A new ligand, naringenin-2-hydroxy benzoyl hydrazone (H(5)L), was prepared by condensation of naringenin with 2-hydroxy benzoyl hydrazine. Its Cu(II), Ni(II), Zn(II) complexes have also been synthesized and characterized on the basis of (1)H-NMR, IR, UV-Vis spectra, elemental analyses, molar conductivity and thermal analyses. The general formula of these complexes was M(H(3)L) [M=Cu(II), Ni(II) and Zn(II)]. In addition, the antioxidant activities (superoxide and hydroxyl radical) of the free ligand and its complexes were determined in vitro. These compounds were found to possess potent antioxidant activity and be better than standard antioxidants like vitamin C and mannitol. In particular, the Cu(II) complex displayed excellent activity on the superoxide radical.     

Synthesis, characterization and DNA-binding studies on La(III) and Ce(III) complexes containing ligand of N-phenyl-2-pyridinecarboxamide

La(III) and Ce(III) complexes containing ligand of N-phenyl-2-pyridinecarboxamide (HL) were synthesized and characterized by elemental analyses, conductivity measurement, IR spectra and thermal analysis. The general formulas of the complexes were [Ln(HL)(3)(H(2)O)(2)](NO(3))(3).2H(2)O [Ln=La(III), Ce(III)]. The results indicated that the oxygen of carbonyl and the nitrogen of pyridyl coordinated to Ln(III), and there were also two water molecules taking part in coordination. Ln(III) and HL formed 1:3 chelate complexes and the coordination number was eight. The interaction between the complexes and DNA was studied by means of UV-vis spectra, fluorescence spectra, SERS spectra and agarose gel electrophoresis. The results showed that complexes can bind to DNA. The binding ability decreased in following order: La(III) complex, Ce(III) complex, and HL. The interaction modes between DNA and the three compounds were found to be mainly intercalative.     

Syntheses and structural analyses of nine-coordinate protonated (Py)2[GdIII(HNta)(Nta)(H2O)] · 5H2O and eight-coordinate (NH4)3[HoIII(Nta)2] complexes

The syntheses and structural determination of Gd(III) and Ho(III) complexes with nitrilotriacetic acids (Nta) were reported in this paper. Their structures and compositions were determined and characterized by single-crystal X-ray structure analyses, elemental analyses, and IR spectra. The first protonated Nta complex was found. Structural analyses indicate that the structure greatly changes, while an alternative Nta ligand was protonated in the ((Py)₂[Gd^III(HNta)(Nta)(H₂O)] · 5H₂O complex and the(NH₄)₃[Ho^III(Nta)₂] complex crystallized as a centrosymmetric structure. By contrast, it is further confirmed that the coordination number and coordinate structure of all trivalent rare-earth metal complexes with aminopolycarboxylic acids mainly depend on the ionic radii and electronic configuration of the central metal ions and their countercations.     

Zn(NO3)2-Leu-H2O体系(25℃)的相平衡及新相配合物的合成与性质

用半微量相平衡方法研究了硝酸锌-亮氨酸-水体系在25℃及全浓度范围内的溶度性质,绘制了体系的相图和饱和溶液折光率曲线,发现并制备了未见报道的非一致溶解配合物[Zn(Leu)(NO3)2(H20)]·H20(A)和Zn(Leu)2(NO3)2·H20(B),通过化学分析、元素分析、IR和TG-DTG等对其组成、结构及热稳定性进行了研究.用精密转动弹热量计测定配合物的标准燃烧能分别为(-12692.80±5.83)和(-15345.71±9.11)J/g,求得它们的标准燃烧焓分别为(-4523.22±2.08)和(-7208.86±4.28)kJ/mol,标准生成焓分别为(-615.67±2.27)和(-1863.16±4.60)kJ/mol     

Structures and ligand exchange of N-confused porphyrin dimer complexes with group 12 metals

N-confused 5,20-diphenylporphyrin (NCDPP, 1) formed 2:2 dimer complexes with group 12 metals both in the solid state and in solution. X-ray single-crystal analyses of the Zn(II) and Cd(II) complexes (7, 8) revealed that each metal ion is coordinated with three inner core nitrogens and a peripheral nitrogen of the other NCDPP in the pair. In the (1)H NMR spectra of 7, 8, and the Hg(II) complex (9), the outer alpha-H signals of the confused pyrrole ring appeared in the upfield region at 2.57, 3.44, and 3.60 ppm, respectively, due to the ring current effect by the coordinated porphyrins. In the case of the Cd(II) and Hg(II) complexes (8, 9), additional magnetic couplings with the metal nuclei of the partner rings were observed. The equilibrium constants (K) of the monomer exchange reaction at 25 degrees C were determined to be 2.5, 1.3, and 0.6 for the (Zn-Cd), (Cd-Hg), and (Zn-Hg) heterodimer complexes, respectively, from the (1)H NMR spectra of a solution containing two different dimers. Furthermore, a metal-transfer reaction from a Zn(II) NCP dimer complex to the free base porphyrin was demonstrated.     

Synthesis,characterization, and antioxidant activities of three Cu(II) complexes with Schiff-base ligands

Cu(II) complexes of three bis(pyrrol-2-yl-methyleneamine) ligands were synthesized and characterized by elemental analyses, mass spectra, and IR spectra. X-ray diffraction analysis shows that [CuL³]₂ is a dinuclear complex with an extremely distorted square-planar geometry. Furthermore, the antioxidant activities of the compounds have been investigated. The electrochemical properties of the Cu(II) complexes have also been studied by cyclic voltammetry. The Cu(II) complexes show similar superoxide dismutase (SOD) activity compared with that of the native Cu, Zn-SOD.     

Synthesis, characterization, antioxidant activity, and DNA-binding studies of 1-cyclohexyl-3-tosylurea and its Nd(III), Eu(III) complexes

A new ligand, 1-cyclohexyl-3-tosylurea (H(2)L), was prepared by condensation ethyl N-(3-tossulfonyl) carbamate and cyclohexanamine. Its two lanthanide(III) complexes, Ln(H(2)L)(3) . 3NO(3) [Ln=Nd (1), and Eu (2)], have been synthesized and characterized on the base of element analyses, ESI-MS, molar conductivities, IR spectra and thermogravimetry/differential thermal analysis (TG-DTA). In addition, the DNA-binding properties of the ligand and its complexes have been investigated by electronic absorption spectroscopy, fluorescence spectroscopy, circular dichroic (CD) spectroscopy and viscosity measurements. The experiment results suggest that the ligand and its two complexes bind to DNA via a groove binding mode, and the binding affinity of the complex 2 is higher than that of the complex 1 and the ligand. Furthermore, the antioxidant activity (superoxide and hydroxyl radical) of the ligand and its metal complexes was determined by using spectrophotometer methods in vitro. These complexes were found to possess potent antioxidant activity and be better than standard antioxidants like vitamin C and mannitol. In particular, complex 2 displayed excellent activity on the superoxide and hydroxyl radical.     

Antimicrobial and antioxidant activities of new metal complexes derived from 3-aminocoumarin

3-Aminocoumarin (L) has been synthesized and used as a ligand for the formation of Cr(III), Ni(II), and Cu(II) complexes. The chemical structures were characterized using different spectroscopic methods. The elemental analyses revealed that the complexes where M=Ni(II) and Cu(II) have the general formulae [ML(2)Cl(2)], while the Cr(III) complex has the formula [CrL(2)Cl(2)]Cl. The molar conductance data reveal that all the metal chelates, except the Cr(III) one, are non-electrolytes. From the magnetic and UV-Visible spectra, it is found that these complexes have octahedral structures. The stability for the prepared complexes was studied theoretically using Density Function Theory. The total energy for the complexes was calculated and it was shown that the copper complex is the most stable one. Complexes were tested against selected types of microbial organisms and showed significant activities. The free radical scavenging activity of metal complexes have been determined by measuring their interaction with the stable free radical DPPH and all the compounds have shown encouraging antioxidant activities.     

系列大环草酰胺配合物的合成与表征——推荐一个综合化学实验

采用加热回流和溶剂热两种方法合成了三种大环草酰胺系列配合物,并对所得配合物进行单晶结构解析。使用元素分析、红外光谱、电子光谱、ESR谱对配合物进行了表征和性质研究。该实验原料简单易得,实验方法简便易行,可操作性强,有利于培养学生的实践能力和创新能力。     

稀土与含硫有机配体配合物的研究: I. 二乙氨基荒酸稀土配合 物Et~2NH~2 [RE9S~2CNEt~2)~4]的合成、表征与结构

在干燥氮气氛中,以乙醇为溶剂制备出稀土与二乙氨基荒酸二乙铵形成的十五个配合物,测定了它们的红外及紫外光谱、热谱和电导,确定该类配合物组成为Et~2NH~2[RE9S~2CNEt~2)~4](RE=La-Lu,Y;Pm除外)。镧配合物的X射线结构分析表明,在该配合物中四个二乙氨基荒酸根各通过两个硫原子与镧离子成键,从而形成八配位的十二面体阴离子,并与二乙铵阳离子形成离子缔合型的配合物分子。     

两种水杨醛型单肟铜(Ⅱ)配合物的合成及结构研究(英文)

2种新的水杨醛型单肟配体HL1(HL1=(E)-2-{1-甲氧基亚氨基甲基}-4,6-二溴苯酚)和HL2(HL2=(E)-2-{1-乙氧基亚氨基甲基}-4-硝基苯酚)分别与一水合乙酸铜反应,合成了2个铜配合物[Cu(L1)2](1)和[Cu(L2)2](2),利用元素分析、红外光谱和紫外光谱等进行了表征,并用X-射线单晶衍射测定了其晶体结构。结果表明,配合物1、2均为单核结构,由1个CuⅡ离子和2个配体组成。中心CuⅡ离子的配位数是4。配合物1为扭曲的平面四边形,而2为规则的平面四边形。配合物1以分子间氢键形成了无限的一维链状超分子结构,而配合物2以分子间氢键和π…π作用形成了二维超分子结构。     

Synthesis,characterization and antimicrobial activity of pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with 2,6-diacetylpyridine bis(trimethylammoniumacetohydrazone)

Pentagonal-bipyramidal isothiocyanato Co(II) and Ni(II) complexes with condensation product of 2,6-diacetylpyridine and trimethylammoniumacetohydrazide (Girard’s T reagent) were synthesized and characterized by elemental analyses, IR and UV–vis spectra, molar conductivity, and magnetic susceptibility. Crystal structures of the Co(II) and Ni(II) complexes were also determined. Antimicrobial activities of the ligand and metal complexes were examined.     

[Cd（SS）（NN）]配合物掺杂CdS的光-电转换特性

本文报道了配合物[Cd(SS)(NN)](SS=mnt2-,1,2-二氰基乙烯-1,2-二硫醇离子.NN=phen-5,6-dione,1,10-菲咯啉-5,6-二酮)的合成.探讨了Cd(SS)(NN)的电子吸收光谱和发射光谱。研究了掺杂有配合物Cd(SS)(NN)的CdS复合膜的光-电转换特性。     

钪、钇硝酸盐与5-Br-PADAP固体配合物的合成及性质研究

关于5-Br-PADAP与金属离子固态配合物的研究,迄今为止国内外未见报导。本文在丙酮中使5-Br-PADAP与硝酸钪及硝酸钇反应,制得了它们的固态配合物。分析了配合物的组成,并对其红外光谱、紫外—可见光谱、溶解性及摩尔电导、差热—热重分析、X光粉末衍射等性质进行了研究。     

Synthesis,interaction with double-helical DNA and biological activity of new Pt(II) and Pd(II) complexes with phenylglycine

The mononuclear palladium(II) (1) and platinum(II) (2) complexes containing phenylglycine have been synthesized and characterized by elemental analysis, IR spectra, and ¹H NMR spectra. The structure of 1 was determined by X-ray diffractometry. The interaction between the complexes and fish sperm DNA (FS-DNA), adenosine-5′-triphosphate (ATP), and adenine (Ade) were investigated by UV absorption spectra, the interaction mode of the complex binding to DNA was studied by fluorescence spectra and viscometry. The results indicate that the two complexes have different binding affinities to DNA, complex 2 > complex 1. Gel electrophoresis assay demonstrates that the two complexes have the ability to cleave pBR322 plasmid DNA. Cytotoxicity experiments were carried out toward four different cancer cell lines, and 1 shows lower inhibitory efficiency than 2, consistent with the binding affinities towards DNA.