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1.
Three new heteroscorpionate ligands, (2‐hydroxyphenyl)bis(imidazol‐1‐yl)methane (HL1), (4‐diethylamino‐2‐hydroxyphenyl)bis(imidazol‐1‐yl)methane (HL2) and (5‐bromo‐2‐hydroxyphenyl)bis(imidazol‐1‐yl)methane (HL3), and their heteroleptic copper(II) complexes of the type [Cu(L1–3)diimine]ClO4 ( 1 – 6 ; where diimine =2,2′‐bipyridyl or 1,10‐phenanthroline) have been synthesized and characterized using spectroscopic methods. The molecular structure of ligand HL1 was determined by single‐crystal X‐ray diffraction. UV–visible, electron paramagnetic resonance and theoretical studies suggest a distorted square pyramidal geometry around copper(II) ion. Analyses of highest occupied and lowest unoccupied molecular orbitals have been used to explain the charge transfer taking place within the complexes. The antioxidant activities of the heteroscorpionate ligands and their heteroleptic copper(II) complexes were determined using ABTS, DPPH and H2O2 free radical scavenging assays with respect to standard antioxidant ascorbic acid. In molecular docking studies, the complexes showed π–π, hydrogen bonding, van der Waals and electrostatic interactions with fibroblast growth factor receptor kinase. In vitro cytotoxicity activities of ligands and copper(II) complexes were examined on human breast adenocarcinoma (MCF‐7), cervical (HeLa) and lung (A549) cancer cell lines and normal human dermal fibroblast cell line using MTT assay. Complex 4 exhibited higher anticancer activity than the other complexes against all three cancer lines, being more potent than the standard drug cisplatin.  相似文献   

2.
Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L1)2]?·?H2O (1), [Ni(L1)2]?·?H2O (2), [Ni(L2)2] (3), and [Co(L3)2]?·?H2O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL1), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL2), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL3) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL1 and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.  相似文献   

3.
Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL1), N-(3-hydroxybenzyl)-alanine acid (HL2), N-(3-hydroxybenzyl)-phenylalanine acid (HL3), and N-(3-hydroxybenzyl)-leucine acid (HL4), were synthesized and characterized on the basis of 1H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L1)2]·2H2O (1), [Cu(L2)2(H2O)] (2), [Cu(L3)2(CH3OH)] (3), and [Cu(L4)2(H2O)]·H2O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?106?M?1, 4.32?×?105?M?1, 5.00?×?105?M?1, and 5.70?×?104?M?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.  相似文献   

4.
Heteronuclear complexes containing oxorhenium(V), with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO2(VI) ions were prepared by the reaction of the complex ligands [ReO(HL1)(PPh3)(OH2)Cl]Cl (a) and/or [ReO(H2L2)(PPh3)(OH2)Cl]Cl (b), where H2L1?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(5,6-diphenyl-1,2,4-triazine-3-ylhydrazone) and H3L2?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(1H-benzimidazol-2-ylhydrazone), with transition and actinide salts. Heterodinuclear complexes of ReO(V) with Fe(III), Co(II), Ni(II), Cu(II) and Cd(II) were obtained using a 1?:?1 mole ratio of the complex ligand and the metal salt. Heterotrinuclear complexes were obtained containing ReO(V) with UO2(VI) and Cu(II) using 2?:?1 mole ratios of the complex ligand and the metal salts. The complex ligands a and b coordinate with the heterometal ion via a nitrogen of the heterocyclic ring and the nitrogen atom of the C=N7 group. All transition metal cations in the heteronuclear complexes have octahedral configurations, while UO2(VI)?complexes have distorted dodecahedral geometry. The structures of the complexes were elucidated by IR, ESR, electronic and 1H NMR spectra, magnetic moments, conductance and TG-DSC measurements. The antifungal activities of the complex ligands and their heteronuclear complexes towards Alternaria alternata and Aspergillus niger showed comparable behavior with some well-known antibiotics.  相似文献   

5.
Thiosemicarbazide copper (II) complexes; [Cu2(HL1)2(H2O)2Cl2].H2O (1) and [Cu2(HL2)2(H2O)2Cl2].2H2O (2) (where H2L1 = 2-picolinoyl-N-(pyridin-2-yl)hydrazine-1-carbothioamide and H2L2 = 2-(2-(2-aminothiazol-4-yl)acetyl)-N-(pyridin-2-yl)hydrazine-1-carbothioamide) have been synthesized and characterized. Analytical and spectroscopic data revealed that ligands behaves as monobasic tetradentate with octahedral geometry. In addition, the optimized geometry of the ligands and their complexes was approved with the Jaguar 9.1 program in the Schrödinger set using DFT (density functional theory) to predict chemical processes and to estimate the properties of the material made by the hybrid functional density system B3LYP. Furthermore, the thermal degradation curves of complexes were discussed in order to determine the kinetic and thermodynamic parameters by various approaches. Additionally, the antioxidant (using the DPPH and SOD methods) and the antibacterial potency of the compounds were examined. Also, docking study of ligands and their complexes was carried out against Staphylococcus aureus gram +ve, gram -ve bacterial strains of Escherichia coli and Candida albicans using the XP glide protocol of Schrödinger suite.  相似文献   

6.
Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HLpz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HLpz?) were synthesized and characterized. The X-ray crystal structures of [Cu2(Lpz)2(4,4?-bipy)(OTf)2] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(Lpz)(py)2]OTf·H2O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(Lpz)(μ2-1,1-N3)]n (3), [Cu(Lpz?)(μ2-1,3-N3)]n (4), and [Cu(HLpz)Cl]n (5) are coordination polymer 1-D chains in the solid state.  相似文献   

7.
Two mononuclear copper(II) complexes with pyrazole derivatives, 1,1′-(anthracen-9-ylmethylene)bis(1H-pyrazole) (L1 ) and 9-(4-(di(1H-pyrazol-1-yl)methyl)phenyl)-9H-carbazole (L2 ), of formulae [CuL1(CH3CN)2](ClO4)2 (1) and [CuL2(CH3CN)2](ClO4)2 (2) were prepared. Both complexes were confirmed by IR, MS, 1H NMR, and elemental analyses. Complex 1 was also characterized by X-ray crystallography, confirming that copper(II) is coordinated by four nitrogen atoms from two L1 and two oxygen atoms from two perchlorates. Furthermore, all ligands and complexes were tested in vitro for their antitumor activities using mouse melanoma cell line B16-F10, HepG2 human hepatoma cell line, and A549 human lung adenocarcinoma cell line. Both complexes displayed potent cytotoxicity and are promising substrates for further investigations.  相似文献   

8.
Mononuclear and trinuclear zinc(II) complexes (1 and 2) with tridentate NNO Schiff-base ligands (HL1?=?N-2-pyridiylmethylidene-4-chloro-2-hydroxy-phenylamine, HL2?=?N-2-pyridiylmethylidene-2-hydroxy-5-chloro-phenylamine) have been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis. The binding properties of zinc(II) complexes with calf thymus DNA (CT-DNA) and HSA were investigated by UV–visible, fluorescence, and circular dichroism spectra. The zinc(II) complexes bind significantly to CT-DNA by intercalation and bind to protein HSA through a static quenching mechanism. The in vitro cytotoxicity of the complexes on human tumor cells lines was assessed by 3-(4,5-dimathylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide, Hoechst 33258 staining experiments.  相似文献   

9.
Two new complexes, [Ni(HL1)(N3)(μ1,1N3)]2 (1) [HL1: NC5H4CH3C=NNH (C=O) NH2] and [Ni(L2)N3] (2) [HL2: NC5H4HC=N NH(C=S)NH2], have been synthesized by reaction of Ni(OAC)2·4H2O and sodium azide with HL1 and HL2 and characterized by elemental analysis, FT-IR, and UV–vis spectral studies. Single-crystal X-ray diffraction reveals that 1 is dinuclear with nickel(II) in an octahedral environment of NNO donors of HL1, two nitrogens of azide bridges and one nitrogen of terminal azide; 2 is mononuclear containing nickel(II) in a distorted square-planar environment of NNS donors of HL2 and one terminal azide. The structures of 1 and 2 have been optimized by density functional theory. The results of antimicrobial activities of ligands, 1 and 2 demonstrated that HL2 and 2 have good antimicrobial activity in contrast with HL1 and 1, related to the presence of sulfur donor in HL2.  相似文献   

10.
Complexation of N-(2-pyridyl)methyl-3-aminopropionic (HL1) and N-(2-pyridyl)methyliminodipropionic (H2L2) acids with copper(II), nickel(II), and cobalt(II) ions is studied. The composition of complexes is determined using the Starik–Barbanel relative yield method. The acid dissociation constants of HL1 and H2L2 are determined potentiometrically; the stability constants of HL1 and H2L2 complexes with metal ions are calculated.  相似文献   

11.
Three new Cu(II) complexes, [Cu(HL1)(pyridine)(H2O)](ClO4)2·2MeOH (1), [Cu2(HL1)2(NO3)2](NO3)2·3H2O (2) and [Cu(HL2)(NO3)2]·MeCN (3), have been synthesized from two Schiff base ligands [HL1 = 1-phenyl-3-((2-(piperazin-4-yl)ethyl)imino)but-1-en-1-ol and HL2 = 4-((2-(piperazin-1-yl)ethyl)imino)pent-2-en-2-ol] using the chair conformer of a flexible piperazinyl moiety. Structural analysis reveals that 1 and 3 are monomeric Cu(II) complexes consisting of five- and six-coordinate Cu(II), respectively, whereas 2 is a dinuclear Cu(II) complex consisting of two different Cu(II) centers, one square planar with the other distorted octahedral. Screening tests were conducted to quantify the binding of 13 towards DNA and BSA as well as the DNA cleavage activity of these complexes using gel electrophoresis. Enzyme kinetic studies were also performed for the complexes mimicking catecholase-like activities. Antibacterial activities of these complexes were also examined towards Methicillin-Resistant Staphylococcus aureus bacteria. The results reflect that 2 is more active than the monomeric complexes, which is further corroborated by density functional theory study.  相似文献   

12.
Two new N2O2 unsymmetrical Schiff bases, H2L1 = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H2L2 = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL1] (1), [CuL2] (2), [NiL1] (3), and [NiL2] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN2O2 coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity.  相似文献   

13.
Four novel ON donor Schiff bases (E)-3-((4-phenoxyphenylimino)methyl)benzene-1,2-diol (HL1),(E)-3-((4-(4-biphenyloxy)phenyliminomethyl)benzene-1,2-diol (HL2), (E)-3-((4-naphthoxyphenylimino)methyl)benzene-1,2-diol (HL3), (E)-3-((4-(2-naphthoxy)phenylimino)methyl)benzene-1,2-diol (HL4) and their copper(II) complexes bis((E)-3-((4-phenoxyphenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L1)2) bis((E)-3-((4-(4-biphenyloxy)phenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L2)2), bis((E)-3-((4-naphthoxyphenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L3)2), bis((E)-3-((4-(2-naphthoxy)phenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L4)2) have been synthesized and characterized by spectroscopic (FTIR, NMR, UV–visible) and elemental analysis. The crystal structures of HL1, HL2, HL3, and HL4 have been determined, which reveal intramolecular N-H?O (HL1, HL2, HL3, and HL4) hydrogen bonds in the solid state. Keto-amine and enol-imine tautomerism is exhibited by the Schiff bases in solid and solution states. The Schiff bases and their copper(II) complexes have been screened for their biological activities. In antimicrobial assays (antibacterial and antifungal), HL4 showed promising results against all strains through dual inhibition property while the rest of the compounds showed activity against selective strains. On the other hand, in cytotoxic, DPPH, and inhibition of hydroxyl (OH) free radical-induced DNA damage assays, the results were found significantly correlated with each other, i.e. the ligands HL1 and HL2 showed moderate activity while their complexes Cu(L1)2 and Cu(L2)2 exhibited prominent increase in activity. As the results of these assays are supporting each other, it represents the strong positive correlation and antioxidant nature of investigated compounds.  相似文献   

14.
Five 2-(1H-benzimidazol-2-yl)-phenol derivatives including 1H (HL1), 5-chloro-(HL2), 5-methyl-(HL3), 5,6-dichloro-(HL4), and 5,6-dimethyl-(HL5) were synthesized by the reaction of their corresponding benzene-1,2-diamine precursors and 2-hydroxybenzaldehyde which subsequently was employed in complexation with Fe(II) to prepare complexes C1C5, respectively. Indeed, in all complexes, the ligands were coordinated as bidentate, via the C=N nitrogen and hydroxy oxygen atom of benzimidazole moiety and phenol ring, respectively. The compounds were characterized by FTIR, UV–vis, 1H- and 13C-NMR spectropscopy, ICP, and elemental analysis (C, H, and N). The purity of these compounds was determined by melting point (m.p )and TLC. The synthesized ligands and complexes were geometrically optimized by Gaussian09 software at B3LYP/TZVP level of theory and satisfactory theoretical–experimental agreement was achieved for analysis of IR data of the compounds. Catalytic behavior of the iron(II) complexes was investigated for ethylene reactivity. On activation with diethylaluminum chloride (Et2AlCl), iron(II) complex (C4) showed the highest activity (1686 kg oligomers.mol?1(Fe).h?1) for ethylene oligomerization when it contains chlorine substituents and exhibits good selectivity for linear 1-butene. The steric and electronic effects of ligands were investigated in detail on the influence of their catalytic activities.  相似文献   

15.
The reaction between tridentate NNO donor hydrazone ligands, (E)-2-cyano-N′-(phenyl(pyridin-2-yl)methylene)acetohydrazide (HL1) and (E)-2-cyano-N′-(1-(pyridin-2-yl)ethylidene)acetohydrazide (HL2), with MnCl2·4H2O in methanol resulted in [Mn(HL1)Cl2(CH3OH)] (1) and [Mn(HL2)Cl2(CH3OH)] (2). Molecular structures of the complexes were determined by single-crystal X-ray diffraction. All of the investigated compounds were further characterized by elemental analysis, FT-IR, TGA, and UV–Vis spectroscopy. These complexes were used as catalysts for olefin oxidation in the presence of tert-butylhydroperoxide (TBHP) as an oxidant. Under similar experimental conditions with equal manganese loading, the presence of [Mn(HL2)Cl2(CH3OH)] (2) resulted in higher conversion than [Mn(HL1)Cl2(CH3OH)] (1).  相似文献   

16.
Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of 2-thiophenecarbonyl hydrazone of 3-isatin (H2L1) and 2-furoic hydrazones of 3-isatin (H2L2) and 3-(N-methyl)isatin (HL3), with general composition [M(L)2] · nX, where X is ethanol or/and water, were synthesised and characterised. The molecular structure of HL3 showed that it crystallised in the keto form, which is also the more abundant tautomer for the three hydrazone ligands in solution. The three ligands behave as κ2-O,N donors in the cobalt(II) and zinc(II) complexes. The X-ray crystal structure of pseudotetrahedral [Zn(HL1)2] · 1.75MeOH confirmed the O,N coordination mode of the two monodeprotonated ligands in their keto forms. Secondary interactions of zinc ions with the O atoms of each isatin keto residue provoke a substantial distortion towards a square pyramidal form. The interaction of the isatin keto residues is stronger in the three nickel(II) complexes where the three acylhydrazones can be considered as κ3-O,N,O donors.  相似文献   

17.
Two Schiff bases, 1-acetylferrocene thiosemicarbazone (HL1) and 1,1′-diacetyl-ferrocene dithiosemicarbazone (H2L2) and their copper(II) complexes were prepared and characterized by elemental analysis, magnetic susceptibility, conductivity, and spectral (IR, UV–Vis, ESR) measurements The IR spectra showed that HL1 acts as neutral or monobasic bidentate ligand, coordinating to copper(II) through either thiono- or thiolo-sulphur and azomethine-N atoms, whereas H2L2 is a neutral or dibasic mononucleating or binucleating quadridentate ligand coordinating through the same atoms. Other spectral measurements indicate that complexes [(L1)2Cu], [(L2)Cu] and [(HL1)2Cu]X2, X?=?Cl, Br or ClO4 have square-planar geometry around copper(II) while [(HL1)CuX2] and [(H2L2)Cu2X4], X?=?Cl or Br, have distorted tetrahedral geometry. The biological activity studies of the complexes and the free ligands towards two gram positive and two gram negative bacteria and one fungal species have been studied and the potential is related to the nature and structure of the tested compounds.  相似文献   

18.
Abstract

A one pot procedure was used to synthesize two new derivatives of α-aminophosphonates. Novel copper(II) complexes of α-aminophosphonates were synthesized by coordinating different copper salts with the newly synthesized α-aminophosphonates. Their structures were characterized by different spectral and analytical techniques. Evaluation of the metal-free ligands HL1, HL2, and their Cu(II) complexes against human colon carcinoma HT-29 cell lines was performed, using cisplatin as a reference drug. The results indicated that the complexes of the ligand HL1 exhibited enhanced anticancer activity, while ligand HL2 complexes showed decreased anticancer activity.  相似文献   

19.
Rehman  F.  Zafar  M. N.  Yousuf  S.  Nazar  M. F.  Mughal  E. U.  Malik  A.  Sumrra  S. H.  Zafar  M. N.  Rafique  H. 《Russian Journal of General Chemistry》2019,89(12):2516-2521

Zn(II) complexes of N-(quinolin-8-yl)picolinamide (HL1) (1) and N2,N6-di(quinolin-8-yl)pyridine-2,6-dicarboxamide (H2L2) (2) have been synthesized by deprotonation of the ligands and characterized by IR, NMR, and Single crystal X-ray crystallography. The mononuclear [Zn(L1)2] (3) and homodinuclear [Zn2(L2)2] (4) complexes are characterized by distorted octahedral geometries stabilized by hydrogen bonding and weak π···π interaction. The complexes demonstrate intense fluorescence bands in comparison with their corresponding ligands with well-distinguished intensity. The complexes act as efficient catalysts in various transesterification reactions. Among those, the best results have been achieved with complex 3 in conversion of 4-nitrophenylacetate into methyl acetate within 3 h.

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20.
Two copper(II) complexes, [Cu2(μ-benzoato)(L1)2]NO3·2H2O (1) and [Cu2(μ-succinato)(L2)2(H2O)]ClO4 (2), have been synthesized, where L1 = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzoylhydrazone and L2 = N′-[(E)-pyridin-2-ylmethylidene]benzoylhydrazone. These complexes were characterized including by single-crystal X-ray diffraction studies. The copper is five-coordinate in 1 while in 2 one copper is five-coordinate and the other is six-coordinate. Electrochemical behavior of these complexes was measured by cyclic voltammetry. The conproportionation equilibrium constants (Kcon) for both complexes have been estimated. The superoxide dismutase (SOD) activities of 1 and 2 were measured by nitro blue tetrazolium assay. Complex 1 has better SOD activity than 2.  相似文献   

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