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1.
4,4′-Bis(chloroacetyl)diphenyl ether (HL) was synthesized from chloroacetyl chloride and diphenyl ether in the presence of AlCl3 as catalyst by Friedel-Crafts reaction. Subsequently, its keto oxime (H2L) and glyoxime (H4L) derivatives were also prepared. Then, five new substituted 4,4′-oxy-bis(aminophenyl-glyoximes) (H4L1–5) were synthesized from 4,4′-oxy-bis(chlorophenylglyoxime) and the corresponding amines. The Ni(II), Cu(II), and Co(II) complexes of these ligands were prepared. The structures of these ligands and their complexes were identified by FT-IR, 1H NMR, and ICP-AES spectral data, elemental analyses, and magnetic measurements.  相似文献   

2.
4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl3 as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H2L) and its sodium chloride complex (H2L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H2L and H2L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, 1H NMR, 13C NMR spectroscopy and elemental analyses data.  相似文献   

3.
A new series of transition metal complexes of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Cd(II), Hg(II), and VO(IV) have been designed and synthesized from the Schiff base derived from cinnamidene-4-aminoantipyrine and 2-aminophenol by involving the carbonyl group of 4-aminoantipyrine. The structural features have been arrived from their elemental analyses, magnetic susceptibility, molar conduction, FAB mass, IR, UV-Vis, 1H NMR and ESR spectral studies. The data show that the complexes have composition of the ML2 type. The UV-Vis, magnetic susceptibility, and ESR spectral data of the complexes suggest an octahedral geometry around the central metal ion except the VO(IV) complex, which has a square-pyramidal geometry. The redox behavior of the copper and vanadyl complexes has been studied by cyclic voltammetry. The antimicrobial activity of the ligand and its complexes has been extensively studied on microorganisms such as Salmonella typhi, Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Aspergillus niger, and Rhizoctonia bataicola. It has been found that most of the complexes have higher activities than that of the free ligand. The nuclease activity of the above metal complexes shows that the complexes cleave DNA through redox chemistry. In the presence of H2O2, the complexes are capable of cleaving calf thymus DNA. The text was submitted by the authors in English.  相似文献   

4.
A new bis(dioxime) ligand (H4L) containing the diphenyl ether moiety has been prepared by reacting 3,3,4,4-tetraaminodiphenyl ether (1) with 2,3-butanedione monoxime (2). Dinuclear copper(II) and cobalt(III) complexes of H4L exhibit a metal–ligand ratio of 2:1 and the ligand coordinates through the 4 nitrogen atoms, as do most bis(dioximes). The [Cu2(H2L)](ClO4)2 molecule coordinates to the other two copper(II) ions through the deprotonated oximate oxygens to yield a tetranuclear structure, doubly-bridged by the oximate groups in a cis arrangement. The structure of bis(dioxime) and its complexes were identified by elemental analyses, 1H-, 13C-n.m.r, i.r and m.s. spectral data.  相似文献   

5.
A new vic-dioxime ligand containing benzophenone hydrazone units, N′-(benzophenone hydrazone)glyoxime [LH2] has been prepared from benzophenone hydrazone and anti-chloroglyoxime in absolute ethanol. Mononuclear nickel(II), cobalt(II), copper(II), zinc(II), and cadmium(II) complexes were also synthesized. Ligand and complexes were characterized by elemental analyses, FT-IR, 1H NMR, and 13C NMR spectroscopy, magnetic moments, and DTA/TG techniques. On the basis of the magnetic and spectral evidences a square-planar geometry for Ni(II) and Cu(II) complexes, tetrahedral for Cd(II) and Zn(II) complexes, and octahedral for Co(II) complex were proposed. Redox behaviors of ligand and its complexes were also investigated by cyclic voltammetry at the glassy carbon electrode.  相似文献   

6.
Sodium4-hydroxy-3-([2-picolinoylhydrazineylidene]methyl)benzenesulfonate (NaH2PH) was synthesized as a novel water-soluble ligand, by the condensation of picolinohydrazide with sodium 3-formyl-4-hydroxybenzenesulfonate. The (NaH2PH) ligand and its isolated Co (II), Fe (III), Hg (II), and Pd (II) complexes were analyzed by elemental analysis and characterized by spectroscopic (Fourier transform infrared spectroscopy, UV–visible, powder XRD, 1H NMR,13C NMR, MS) and magnetic measurements. By comparing IR spectra of both ligand and the metal complexes, one can assume that the (NaH2PH) ligand behaves as a bi-negative tetradentate (ONNO) in [Co (NaPH)(H2O)2].3H2O, and a mono-negative tridentate (ONO) in [Fe (NaPH)Cl2(H2O)] complex, whereas in [Hg2(NaPH)Cl2(H2O)] complex, (NaH2PH) coordinates as a bi-negative pentadentate (ONNNO) ligand via deprotonated OH group of phenolic ring (C=N)Py and (C=N*) coordinated to one of Hg (II) ion and the oxygen atom of enolic group and (C=N)az group with the another Hg (II) ion. Moreover, (NaH2PH) acts as bi-negative tridentate (ONO) ligand in [Pd (NaPH)(H2O)].2H2O complex. The geometries of complexes were suggested based on the UV–visible spectra, magnetic measurements and confirmed by applying discrete Fourier transform (DFT) optimization studies. The thermal fragmentation of both [Pd (NaPH)(H2O)].2H2O and [Co (NaPH)(H2O)2].3H2O complexes was performed, and the kinetic and thermodynamic parameters were computed using the Coats–Redfern and Horowitz–Metzger methods. The redox behavior of divalent ions of cobalt and mercury were discussed by the cyclic voltammetry technique in the presence and absence of (NaH2PH) ligand. Biological potencies of the ligand and its metal complexes were evaluated as antioxidants (ABTS and DPPH), anticancer, DNA, and antimicrobial (Staphylococcus aureus and Bacillus subtilis as Gram (+) bacteria, Escherichia coli and Pseudomonas aeruginosa as Gram (−) bacteria, and Candida albicans as fungi).  相似文献   

7.
N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H2L) and its sodium chloride complex (H2L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H2L and H2L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF2+-capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, 1H NMR spectroscopy and elemental analyses data.  相似文献   

8.
Reactions of 1,2-di(o-aminophenylthio)ethane with 3-ethoxy-2-hydroxybenzaldehyde yield the new hexadentate N2S2O2 donor thioether Schiff base 1,2-bis(2-((2-(thio)phenylimino)methyl)-6-ethoxyphenol)ethane (H2L). Ni(II), Zn(II), Cd(II), and Hg(II) complexes of this ligand were prepared. Of these complexes, [NiL]·2H2O has been structurally characterized by X-ray crystallography. The coordination geometry around Ni(II) was described as octahedral. Zn(II), Cd(II), and Hg(II) complexes and the Schiff base ligand have been characterized by CHN analyses, molar conductivity, UV–vis, FT-IR, 1H, and 13C NMR spectroscopy.  相似文献   

9.
Novel transition metal complexes with the repaglinide ligand [2-ethoxy-4-[N-[1-(2piperidinophenyl)-3-methyl-1-1butyl] aminocarbonylmethyl]benzoic acid] (HL) are prepared from chloride salts of manganese(II), iron(III), copper(II), and zinc(II) ions in water-alcoholic media. The mononuclear and non-electrolyte [M(L)2(H2O)2]?nH2O (M = Mn2+, n = 2, M = Cu2+, n = 5 and M = Zn2+, n = 1) and [M(L)2(H2O)(OH)]?H2O (M = Fe3+) complexes are obtained with the metal:ligand ratio of 1:2 and the L-deprotonated form of repaglinide. They are characterized using the elemental and molar conductance. The infrared, 1H and 13C NMR spectra show the coordination mode of the metal ions to the repaglinide ligand. Magnetic susceptibility measurements and electronic spectra confirm the octahedral geometry around the metal center. The experimental values of FT-IR, 1H, NMR, and electronic spectra are compared with theoretical data obtained by the density functional theory (DFT) using the B3LYP method with the LANL2DZ basis set. Analytical and spectral results suggest that the HL ligand is coordinated to the metal ions via two oxygen atoms of the ethoxy and carboxyl groups. The structural parameters of the optimized geometries of the ligand and the studied complexes are evaluated by theoretical calculations. The order of complexation energies for the obtained structures is as follows:
$$Fe(III) complex < Cu(II) complex < Zn(II) complex < Mn(II) complex.$$
The redox behavior of repaglinide and metal complexes are studied by cyclic voltammetry revealing irreversible redox processes. The presence of repaglinide in the complexes shifts the reduction potentials of the metal ions towards more negative values.
  相似文献   

10.
Series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes were prepared with tetradentate Schiff base ligand derived by condensation of 2‐aminophenol with dibenzoylmethane. The novel Schiff base H2L (2–2′‐((1Z,1Z’)‐(1,3‐diphenyl propane‐1,3 diylidene) bis (azanylylidene) diphenol) and its binary metal complexes were characterized by physicochemical procedures i.e. elemental analysis, FT‐IR, UV–Vis, thermal analyses (TGA/DTG), mass spectrometry, magnetic susceptibility and conductometric measurements. On the basis of these studies, an octahedral geometry for all these complexes was proposed expect Ni(II) complex which had tetrahedral geometry. Molar conductivity values revealed that the complexes were electrolytes except Mn(II), Zn(II) and Cd(II) complexes were non electrolytes. The ligand bound to the metal ions via two azomethine N and two phenolic OH as indicated from the IR and 1H NMR spectral study. The molecular and electronic structures of H2L and its zinc complex were optimized theoretically and the quantum chemical parameters were calculated. The antimicrobial activity against a number of bacterial organisms as Streptococcus pneumonia, Bacillus Subtilis, Pseudomonas aeruginosa and Escherichia coli and fungi as Aspergillus fumigates, Syncephalastrum racemosum, Geotricum candidum and Candida albicans by disk diffusion method were screened for the Schiff base and its complexes. The Cd(II) complex has potent antimicrobial activity. Anticancer activity of the Schiff base ligand and its metal complexes were evaluated in human cancer (MCF‐7 cells viability). The Cr(III) complex exhibited higher activity than other complexes and ligand. Molecular docking was used to predict the binding between Schiff base ligand (H2L) and its Zn(II) complex and the receptors of RNA of amikacin antibiotic (4P20) and human‐DNA‐Topo I complex (1SC7). The docking study provided useful structural information for inhibition studies.  相似文献   

11.
This article reports the synthesis and characterization of four Ni(II) Schiff base complexes, [Ni(L)(H2O)], where H2L = N-(dehydroacetic acid)-thiosemicarbazide (H2dha-tsc), N-(dehydroacetic acid)-4-methyl-3-thiosemicarbazide (H2dha-mtsc), N-(dehydroacetic acid)-4-phenyl-3-thiosemicarbazide (H2dha-ptsc), or N-(dehydroacetic acid)-4-phenylsemicarbazide (H2dha-psc). The nature of bonding and stereochemistry of these complexes have been deduced from elemental analysis, infrared and electronic spectral studies, molar conductance, magnetic measurements, mass spectrometry, thermogravimetric analysis, 1H NMR and 13C NMR studies, and cyclic voltammetry. The stabilities of the complexes were determined in both solid state and solution. Molecular geometry optimizations and vibrational frequency calculations were performed with Gaussian 09 software package using density functional theory (DFT) with B3LYP/6-311G for a ligand (dha-ptscH2) and B3LYP/LANL2DZ combination for [Ni(dha-mtsc)(H2O)]. Based on the combined experimental and theoretical studies, square planar geometry has been proposed for the Ni(II) complexes. The Schiff base ligands and their metal complexes were screened for antibacterial activities against gram-negative bacteria (Escherichia coli ) at different concentrations to get their minimum inhibition concentration values. The bactericidal activity was enhanced in metal complexes as compared to free ligands.  相似文献   

12.
The new Co(II), Cu(II), Ni(II) and Zn(II) complexes of potentially N2O2 Schiff base ligand [N,N’-bis(salicyldehydene)-1,4-bis-(o-aminophenoxy)butane] (H2L) prepared from 1,4-bis-(o-aminophenoxy)butane and salicyldehyde in DMF. Microanalytical data, elemental analysis, magnetic measurements, lH NMR, 13C NMR, UV-visible and IR spectra as well as conductance measurements were used to confirm the structures. In all complexes, H2L behaves as a tetradentate. The article is published in the original.  相似文献   

13.
The reaction of copper(II) salts with (E)-N-(2-hydroxy-1,2-di(pyridin-2-yl)ethylidene)aroyl hydrazide (H2L1, H2L2, H3L3) or (E)-N-(2-hydroxy-1,2-di(pyridin-2-yl)ethylidene) isonicotinohydrazide (H2L4) afforded the complexes [(L)Cu(H2O)3], [(H2L)Cu(OAc)(H2O)], [(HL)Cu(OAc)] n , [(H2L)Cu(H2O)](ClO4)2 and [(H2L)Cu(OAc)(H2O)], where n = 1 or 2 and L is the dinegative ion of the ligands. The ligands and their complexes are characterized by elemental analyses, spectral (IR, NMR, electronic, and ESR) and magnetic studies. The FT-IR indicates that the ligands are neutral or anionic polydentate. The number of the coordinating centers depends on the nature of the metal used and the reaction conditions. The room temperature magnetic moment values, electronic spectra and ESR data indicate square planar, trigonal bipyramidal, square pyramidal, and distorted octahedral ligand fields around copper(II). Thermal decomposition of the complexes was monitored by TG and DTG under N2 and the thermal decomposition mechanisms are given. The compounds were screened for their antimicrobial activities on some Gram-positive and Gram-negative bacterial species. The free ligands are inactive against all studied bacteria. The complexes have variable activity with the most active [(H2L)Cu(H2O)](ClO4)2, where H2L is H2L1 or H2L2. The minimum inhibition concentrations for these two complexes were determined. These biological activity results are related to the structures of the compounds.  相似文献   

14.
Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-p-tolylglyoxime (L1H2), tert-butyl amine-p-tolylglioxime (L2H2) and sec-butylamine-p-tolylglyoxime (L3H2), have been prepared. The metal to ligand ratios of the complexes were found to be 1?:?2. The Cu(II) complexes of these ligands are proposed to be square planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF, CHCl3 and C2H5OH. The ligands have been characterized by elemental analysis, IR, UV-VIS, 1H?NMR, 13C?NMR and thermogravimetric analysis (TGA). The complexes were characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements, thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal complexes show quasi-reversible one-electron redox processes. However, Co(L1H)2 and Cu(L1H)2 complexes show another oxidation peak in the positive region. This single irreversible oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron transfer rates of metal complexes with L1H2 are higher than the other complexes.  相似文献   

15.
This paper presents a new azacrown containing vic-dioxime; anti-N-(4-aminophenyl)aza-15-crown-5-glyoxime (LH2), and its mononuclear nickel(II), copper(II), cobalt(II), cadmium(II) and zinc(II) complexes. The azacrown moieties appended at the periphery of the oxime provide solubility for the vic-dioxime ligand and complexes in common organic solvents. The mononuclear M(LH)2 (M = Ni and Cu), M(LH)2(H2O)2 (M = Co) and [M(LH)(H2O)(Cl)] (M = Cd and Zn) complexes have been obtained with the metal:ligand ratios of 1:2 and 1:1. The structure of the ligand is confirmed by elemental analysis, Fourier transform infrared (FT-IR), ultraviolet-visible (UV-Vis), mass spectrometry (MS), one-dimensional (1D) 1H, 13C NMR, distortionless enhancement by polarization transfer (DEPT) and two-dimensional (2D) heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) techniques. The structures of the complexes are confirmed by elemental analyses, MS, UV-Vis, FT-IR and 1H, 13C NMR techniques. Redox behaviors of the ligand and its complexes have been investigated by cyclic voltammetry at the glassy carbon electrode in 0.1 M TBATFB in DMSO. The antibacterial activity was studied against Staphylococcus aureus ATCC 29213, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Lactobacillus acidophilus RSHM 06029, Escherichia coli ATCC 25922, Pseudomonasaeruginosa ATCC 27853. The antimicrobial test results indicate that all the complexes have low levels of antibacterial activity against both Gram negative and Gram positive bacterial species.  相似文献   

16.
New N2O2 donor type Schiff bases have been designed and synthesized by condensing acetylaceto-4-aminoantipyrine/acetoacetanilido-4-aminoantipyrine with 2-amino benzoic acid in ethanol. Solid metal complexes of the Schiff bases with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, FAB Mass, IR, UV-Vis., 1H NMR, and ESR spectral studies. The data show that the complexes have a composition of the ML type. The UV-Vis., magnetic susceptibility, and ESR spectral data of the complexes suggest a square planar geometry around the central metal ion, except for VO(IV) complexes, which have square-pyramidal geometry. The redox behavior of copper and vanadyl complexes has been studied by cyclic voltammetry. The nuclease activity of the above metal complexes shows that the complexes cleave DNA through redox chemistry. In the presence of H2O2, all the complexes are capable of cleaving calf thymus DNA plasmids, in order to compare the cleavage efficiency of all metal complexes in the two different ligand environments. In this assay, Cu(II), Ni(II), Co(II), and Zn(II) exhibit more cleavage efficiency than other metal ions. This article was submitted by the authors in English.  相似文献   

17.
A new series of Cu(II), Ni(II), and Co(II) complexes have been synthesized from 3-formylchromoniminopropylsilatrane (C19H24O5N2Si) (2) and 3-formylchromoniminopropyltriethoxysilane (1). Silatrane ligand (C19H24O5N2Si) (2) has been synthesized by the reaction between 3-aminopropyltriethoxysilane and 3-formylchromone followed by a treatment with triethanolamine. The nature of bonding and the geometry of the complexes have been deduced from elemental analyses, magnetic susceptibility, infrared, electronic, 1H NMR, 13C NMR, and ESR spectral studies. The electronic absorption spectra and magnetic susceptibility measurements of the complexes indicate square planar geometry for Cu(II) and Ni(II) and tetrahedral geometry for Co(II). The redox behavior of copper complexes was studied by cyclic voltammetry. The biological activity of the ligand and metal complexes has been studied on Klebsiella pneumoniae, Staphylococcus aureus, Escherichia Coli, and Bacillus subtilis by the well diffusion method using acetonitrile as solvent. The zone of inhibition values were measured at 37°C for 24 h. Antimicrobial screening tests show better results for the metal complexes than the ligand.  相似文献   

18.
New complexes, [Fe(L)Cl], [Ni(L)], and [Zn(L)C2H5OH] (1–3), were synthesized by template reaction of 2-hydroxy-acetophenone-S-methyl-thiosemicarbazone with 2-hydroxy-benzaldehyde. The compounds were characterized by elemental analysis, magnetic measurements, FT-IR, 1H NMR, UV–visible, and ESI–MS spectra. In these complexes, the ligand is coordinated to the metal ion as dinegatively charged tetradentate chelating agents via the N2O2 donor set. The iron(III) and zinc(II) complexes exhibit square pyramidal geometry whereas the nickel(II) complex has a square planar geometry. The crystal structure of 1, determined by X-ray diffraction method, indicates that 1 crystallizes in the monoclinic space group P21/c with Z = 4. Thermal decompositions of the compounds have been investigated using TGA in air.  相似文献   

19.
A novel Schiff base ligand (H2L) was prepared through condensation of 2,6‐diaminopyridine and o‐benzoylbenzoic acid in a 1:2 ratio. This Schiff base ligand was characterized using elemental and spectroscopic analyses. A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal complexes of H2L were prepared and characterized using elemental analysis, spectroscopy (1H NMR, mass, UV–visible, Fourier transform infrared, electron spin resonance), magnetic susceptibility, molar conductivity, X‐ray powder diffraction and thermal analysis. The complexes are found to have trigonal bipyramidal geometry except Cr(III), Mn(II) and Fe(III) complexes which have octahedral geometry based on magnetic moment and solid reflectance measurements. The infrared spectral studies reveal that H2L behaves as a neutral bidentate ligand and coordinates to the metal ions via the two azomethine nitrogens. 1H NMR spectra confirm the non‐involvement of the carboxylic COOH proton in complex formation. The presence of water molecules in all reported complexes is supported by thermogravimetric studies. Kinetic and thermodynamic parameters were determined using Coats–Redfern and Horowitz–Metzger equations. The synthesized ligand and its complexes were screened for antimicrobial activities against two Gram‐positive bacteria (Bacillus subtilis and Staphylococcus aureus), two Gram‐negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and one fungus (Candida albicans). Anticancer activities of the ligand and its metal complexes against human breast cancer cell line (MCF7) were investigated. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

20.
A novel ligand 3‐(1H‐imidazo[4,5‐f][1,10]phenanthrolin‐2‐yl)‐4H‐1‐benzopyran‐4‐one (ipbp) and its ruthenium(II) complexes [Ru(bpy)2(ipbp)]2+ ( 1 ) and [Ru(ipbp)(phen)2]2+ ( 2 ) (bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline) were synthesized and characterized by elemental analysis and mass, 1H‐NMR, and electronic‐absorption spectroscopy. The electrochemical behavior of the complexes was studied by cyclic voltammetry. The DNA‐binding behavior of the complexes was investigated by spectroscopic methods and viscosity measurements. The results indicate that complexes 1 and 2 bind with calf‐thymus DNA in an intercalative mode. In addition, 1 and 2 promote cleavage of plasmid pBR 322 DNA from the supercoil form I to the open circular form II upon irradiation.  相似文献   

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