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1.
Mononuclear copper(II), cobalt(II) and nickel(II) complexes of cetirizine (CTZ = 2-[2-[4-[(4-chlorophenyl)phenyl methyl]-piperazine-1-yl]-ethoxy]acetic acid) in the presence of 2-aminomethyl-benzimidazole·2HCl (AMBI), as a representative example of heterocyclic bases, were synthesized and studied by different physical techniques. All mixed-ligand complexes have been fully characterized with the help of elemental analyses, molecular weight determinations, molar conductance, magnetic moments and spectroscopic data. The formulae of the isolated complexes are [M(AMBI)(CTZ)(NO3)(H2O)2nH2O where AMBI is the neutral bidentate 2-aminomethylbenzimidazole, CTZ the deprotonated cetirizine and n = 1 for Co(II) or 0 for Cu(II) and Ni(II) complexes. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytes. The formation equilibria of the ternary complexes have been investigated. Ternary complexes are formed by a simultaneous mechanism. Stoichiometry and stability constants for the complexes formed are reported. The concentration distribution of the complexes in solution was evaluated as a function of pH. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The synthesized metal chelates have been screened for their antimicrobial activities against the selected types of Gram-positive (G+) and Gram-negative (G?) bacteria. They were found to be more active against Gram positive than Gram negative bacteria. The antimicrobial activity in terms of metal ions obeys this order: Cu(II) > Ni(II) > Co(II).  相似文献   

2.

Heterobi- and tri-nuclear complexes [LMM'Cl] and [(LM) 2 M'](M=Ni or Cu and M'=Mn, Fe or Co) have been synthesised. The heteronuclear complexes were prepared by stepwise reactions using two mononuclear Ni(II) and Cu(II) complexes of the general formula [HLM]·1/2H 2 O, as ligands towards the metal ions, Mn(II), Fe(III) and Co(II). The asymmetrical pentadentate (N 2 O 3 ) Schiff-base ligands used were prepared by condensing acetoacetylphenol and ethylenediamine, molar ratio 1 1, to yield a half-unit compound which was further condensed with either salicylaldehyde or naphthaldehyde to yield the ligands H 3 L 1 and H 3 L 2 which possess two dissimilar coordination sites, an inner four-coordinate N 2 O 2 donor set and an outer three-coordinated O 2 O set. 1 H NMR and IR spectra indicate that the Ni(II) and Cu(II) ions are bonded to the inner N 2 O 2 sites of the ligands leaving their outer O 2 O sites vacant for further coordination. Different types of products were obtained according to the type of metal ion. These products differ in stoichiometry according to the type of ligand in the parent compound. Electronic spectra and magnetic moments indicate that the structures of the parent Ni(II) and Cu(II) complexes are square-planar while the geometry around Fe(III), Mn(II) and Co(II) in their products are octahedral as elucidated from IR, UV-visible, ESR, 1 H NMR, mass spectrometry and magnetic moments.  相似文献   

3.
Three new diclofenac‐based copper(II) complexes, namely tetrakis{μ‐2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O:O′}bis(methanol‐κO)copper(II), [Cu2(μ‐dicl)4(CH3OH)2] ( 1 ), bis{2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O,O′}bis(1‐vinyl‐1H‐imidazole‐κN3)copper(II), [Cu(dicl)2(vim)2] ( 2 ), and bis{2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O,O′}bis(1H‐imidazole‐κN3)copper(II), [Cu(dicl)2(im)2] ( 3 ) [dicl is diclofenac (C14H10Cl2NO2), vim is 1‐vinylimidazole (C5H6N2) and im is imidazole (C3H4N2)], have been synthesized and characterized by elemental analysis, FT–IR spectroscopy, thermal analysis and single‐crystal X‐ray diffraction. X‐ray diffraction analysis shows that complex 1 consists of dimeric units in which the dicl ligand exhibits a bidentate syn,syn‐μ2 coordination mode linking two copper(II) centres. Complexes 2 and 3 have mononuclear units with the general formula [Cu(dicl)2L2] (L is vim or im) in which the CuII ions are octahedrally coordinated by two L and two dicl chelating ligands. The L and dicl ligands both occupy the trans positions of the coordination octahedron. The different coordination modes of dicl in the title complexes were revealed by Fourier transform IR (FT–IR) spectroscopy. The spin matching between the copper(II) centres in the dimeric [Cu2(μ‐dicl)4(CH3OH)2] units was also confirmed by magnetic data to be lower than the spin‐only value and electron paramagnetic resonance (EPR) spectra. The thermal properties of the complexes were investigated by thermogravimetric (TG) and differential thermal analysis (DTA) techniques.  相似文献   

4.
Three Cu(II) halido complexes of 3-pyridinepropanol (3-pyprop), 2-pyridineethanol (2-pyet), and 2-pyridinemethanol (2-pymet) have been prepared and investigation of their crystal structures undertaken. All the reported products contain simple pyridine alcohols as neutral ligands. Cu(3-pyprop)2Br2, 1, exhibits square-planar coordination geometry with the axial sites involved in weak bridging contact with the neighboring units to form infinite chains. Reaction of CuBr2 with 2-pyet leads to an ionic complex [Cu(2-pyet)2Br]Br, 2, with distorted square-pyramidal coordination environment: the Cu center in the cation is surrounded by two 2-pyet ligands, coordinated in chelating manner, and a bromide. Reaction of CuCl2 with 2-pymet resulted in the formation of a dinuclear ionic complex Cu2(2-pymet)4Cl2]Cl2·2H2O, 3. The centrosymmetric cation consisted of two Cu ions doubly bridged by chlorides and coordinated by chelating 2-pymet ligands. The positive charge is balanced by free chlorides involved in hydrogen bonds with the lattice water molecules.  相似文献   

5.
"Tritopic" picolinic dihydrazone ligands with tridentate coordination pockets are designed to produce homoleptic [3 x 3] nonanuclear square grid complexes on reaction with transition-metal salts, and many structurally documented examples have been obtained with Mn(II), Cu(II), and Zn(II) ions. However, other oligomeric complexes with smaller nuclearities have also been discovered and identified structurally in some reactions involving Fe(II), Co(II), Ni(II), and Cu(II), with certain tritopic ligands. This illustrates the dynamic nature of the metal-ligand interaction and the conformationally flexible nature of the ligands and points to the possible involvement of some of these species as intermediates in the [3 x 3] grid formation process. Examples of mononuclear, dinuclear, hexanuclear, heptanuclear, and nonanuclear species involving Fe(II), Co(II), Ni(II), and Cu(II) salts with a series of potentially heptadentate picolinic dihydrazone ligands with pyrazine, pyrimidine, and pyridine end groups are described in the present study. Iron and cobalt complexation reactions are complicated by redox processes, which lead to mixed-oxidation-state Co(II)/Co(III) systems when starting with Co(II) salts, and reduction of Fe(III) to Fe(II) when starting with Fe(III). Magnetic exchange within the polynuclear structural frameworks is discussed and related to the structural features.  相似文献   

6.
Nickel(II) and copper(II) complexes of two unsymmetrical tetradentate Schiff base ligands [Ni(Me-salabza)] (1), [Cu(Me-salabza)] (2) and [Ni(salabza)] (3), {H2salabza = N,N′-bis[(salicylidene)-2-aminobenzylamine] and H2Me-salabza = N,N′-bis[(methylsalicylidene)-2-aminobenzylamine]}, have been synthesized and characterized by elemental analysis and spectroscopic methods. The crystal structures of 2 and 3 complexes have been determined by single crystal X-ray diffraction. Both copper(II) and nickel(II) ions adopt a distorted square planar geometry in [Cu(Me-salabza)] and [Ni(salabza)] complexes. The cyclic voltammetric studies of these complexes in dichloromethane indicate the electronic effects of the methyl groups on redox potential.  相似文献   

7.
The free Schiff bases H2MABCE, H2MABCP, and H2MABCT and their complexes [Ni(MABCE)], [Ni(MABCP)], [Ni(MABCT)], [Cu(MABCE)], [Cu(MABCP)], and [Cu(MABCT)] have been synthesized and characterized by spectroscopic, cyclic voltammetric, and thermal studies. The geometry around nickel is square planar with N2O2 donor atoms. Cyclic voltammetric studies of the Ni(II) complexes show one-electron quasi-reversible waves corresponding to Ni(II)/Ni(I) and Ni(II)/Ni(III) processes. The Cu(II) complexes exhibit an irreversible well defined one electron transfer reduction peak in the range of ?0.34 to ?1.08 V. The electronic spectra of the complexes suggest a four-coordinate geometry. The crystal structure of the ligand H2MABCT and the complex [Ni(MABCP)] have also been reported. The mean Ni–N and Ni–O bond distances are Ni–N = 1.849(4) and Ni–O = 1.837(4) Å.  相似文献   

8.
A new ligand, 4-chloromethyl-2-(2-hydroxybenzilidenehydrazino) thiazole, has been synthesized from dicholoroacetone and 2-hydroxybenzylidenethiosemicarbazon. Metal complexes of the ligand were prepared from acetate salts of Co(II), Cu(II), Ni(II) and chloride of Cr(III) in dry acetone. Characterization of the ligand and its complexes was made by microanalyses, FT-IR, 13C, 1H NMR and UV-vis spectroscopy, magnetic susceptibility and thermogravimetric analysis. In the light of these results, it was suggested that two ligands coordinate to each metal atom by hydroxyl oxygen, imino nitrogen and thiazole ring nitrogen to form high spin octahedral complexes with Cr(III), Co(II), Ni(II) and Cu(II).  相似文献   

9.
A series of novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with oxaprozin (Hoxa), a non-steroidal anti-inflammatory drug, has been synthesized. The drug and complexes have been characterized by elemental and thermogravimetric (TG) analysis, Fourier transform (FT)-IR, 1H-NMR, 13C-NMR, UV-Vis spectroscopy and magnetic susceptibility measurements. The (pseudo)octahedral geometry has been proposed for all complexes based on electronic spectra and magnetic moments. With exception of the Cu(II) complex, where bridging bidentate mode of COO groups has been found, FT-IR spectra confirmed chelately coordinated COO groups in the other complexes. The general formula of the complexes is [M(H2O)2(oxa)2 ·χH2O, with χ=2 for M=Mn, Co and Ni and χ=1.5 for Zn. The binuclear Cu(II) complex, [Cu2(H2O)2(OH)(oxa)3]·2H2O, has strong Cu-Cu interactions of antiferromagnetic type. The complexes and Hoxa did not exhibit the cytotoxic effect to peritoneal macrophages. For the first time these complexes have been tested for their in vitro antiproliferative activity against human colon and breast cancer cell lines, HCT-116 and MDA-231, respectively. For all investigated compounds significant antiproliferative effects have been observed. Ni(II) complex has been shown to be a promising antiproliferative agent exerting excellent activity against HCT-116 even in nanomolar concentrations.  相似文献   

10.
Three new metal complexes of 4,6-bis(4-chlorophenyl)-2-amino-1,2-dihydropyridine-3-carbinitrile (L) with Co(II), Ni(II) and Cu(II) were synthesized and characterized with physicochemical and spectroscopic techniques. The data suggest that (L) acts as a bidentate ligand bound to the divalent metal ions through amino N and carbinitrile N atoms having [M(L)2(H2O)2]2+ formula (M = metal ions). The theoretical parameters, model structures, charges and molecular orbitals of all possible complexes have been determined using density functional theory. The energy gap of free ligand is ?E = 0.12565 eV, and this value is greater than energy gap of complexes, which indicates that the complexes are more reactive than free ligand. Also, ?E of Co(II) complex is lower than other complexes, which indicates that Co(II) complex is more reactive than Ni(II) and Cu(II) complexes. The antibacterial and antifungal activities of the ligand, metal salts and its complexes were tested against some microorganisms (bacteria and fungi). The complexes showed increased antibacterial and antifungal profile in comparison with the free ligand.  相似文献   

11.
Three novel ferrocenyl Schiff base ligands containing pyridine moiety have been formed by 1:2 molar condensation of 1,1′‐diacetylferrocene with 2‐aminopyridine, 2‐amino‐5‐picoline or 2‐amino‐5‐chloropyridine, respectively. The ligands are 1,1′‐bis[1‐(pyridyl‐2‐imino)‐ethyl]ferrocene (L1); 1,1′‐bis[1‐(5‐methyl‐pyridyl‐2‐imino)ethyl]ferrocene (L2) and 1,1′‐bis[1‐(5‐chloropyridyl‐2‐imino)ethyl]ferrocene (L3). These ligands form 1:1 complexes with Co(II), Cu(II), Ni(II) and Zn(II) ions. The prepared ligands and their complexes have been characterized by IR, 1H NMR, 13C NMR, UV/Vis spectra as well as elemental analysis. The spectral data of the ligands and their complexes are discussed in connection with the structural changes due to complexation.  相似文献   

12.
The biological and optical importance of the o-aminoaldehyde family of ligands inspired us to evaluate the coordination properties and biological activities of 2-aminonicotinaldehyde (ANA). Here, we report the synthesis, characterization, biological screening and molecular docking studies of ANA and its metal complexes of Ni(II), Pd(II), Co(II) and Cu(II) using various analytical and spectroscopic techniques. The single crystal X-ray diffraction studies of ANA explain the solid-state assembly and an interesting supramolecular herring bone stacking pattern by classical N–H···O/N intra/inter molecular and non-classical C–H···O/N intermolecular H-bonding. ANA and its metal complexes were screened for in vitro anticancer, antimicrobial and anti-oxidant activities. Anticancer activity was tested against HeLa, MCF-7 and HEK293 human cancer cell lines. The [Ni(ANA)2Cl2] complex showed good activity against HeLa and MCF-7, the [Pd(ANA)2Cl2] and [Cu(ANA)2Cl2] complexes against HeLa, and the [Co(ANA)2Cl2] complex against MCF-7. In antimicrobial screening, the [Co(ANA)2Cl2] and [Cu(ANA)2Cl2] complexes were proved to be potent antibacterial and antifungal agents. The anti-oxidant activity of these complexes was investigated through DPPH radical assay, and it was found that all the complexes have good radical scavenging capability. Molecular docking studies were also carried for all the metal complexes against EGFR as a target protein by using Autodock, and the results strongly correlated with the anticancer activity.  相似文献   

13.
Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of salicylidene-N-cyano-acetohydrazone H2L1 and 2-hydroxy-l-naphthylidene-N-cyanoacetohydrazone H2L2 have been prepared in ethanolic solution and characterized by analytical, spectral, magnetic susceptibility, molar conductivity and TGA measurements. The analytical data show that all the complexes derived from H2L1 and H2L2 are formed in molar ratios 1M:2L, except the complexes of Mn(II), Co(II) and Cu(II) acetates of H2L2 and the complexes of Mn(II), Co(II) and Ni(II) acetates and CuCl2 of H2L1 are formed in 1:1 molar ratios. The conductance data show that all metal complexes are non-electrolytes. Electronic absorption spectra and magnetic susceptibility measurements proved that the prepared complexes have octahedral configuration except [Co(HL2)OAc] which has tetrahedral structure. The ligand field parameters were calculated for the Co(II) and Ni(II) complexes and the data show that the covalent character of the metal ligand sigma-bond is low. The ESR parameters of the Cu(II) complexes at room temperature were calculated. Thermal TGA for some solid complexes are reported.  相似文献   

14.
Proton-ligand association constants of 1-benzoyl(1,2,4-triazol-3-yl)thiourea (BTTU) and its complex formation constants with some bivalent metal ions Ni(II), Co(II), Mn(II), Zn(II), and Cu(II), have been determined potentiometrically in 50% EtOH–H2O and 0.1 M NaNO3. The complexes formed in solution have a stoichiometry of 1:1 and 1:2 [M:L], where M represents the metal ion and L the BTTU ligand. The corresponding thermodynamic parameters are derived and discussed. The complexes are stabilized by enthalpy changes and the results suggest that complexation is an enthalpy-driven process. The effects of metal ion, ionic radius, electronegativity, and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3d transition metals follow the order Mn2+ < Co2+ < Ni2+ < Cu2+ > Zn2+. The metal complexes were synthesized and characterized by elemental analyses, conductance, IR, 1H NMR, and magnetic measurements. The low magnetic moment of 0.11 BM for the Cu(II) complex is suggestive of dimerization through Cu–Cu interaction. The concentration distribution diagrams of the complexes were evaluated. The ligands and their metal complexes have been screened in vitro against some bacteria and fungi.  相似文献   

15.
The complexes of 3,5-dimethoxybenzoates of Co(II), Ni(II) and Cu(II) have been synthesized as hydrated polycrystalline solids and characterized by elemental analysis, IR, FIR and electronic spectroscopy, magnetic studies and X-ray diffraction measurements. They possess colours typical of the M(II) ions: Cu-blue, Ni-green, Co-pink. The carboxylate groups bind as monodentate or a symmetrical, bidentate chelating or bridging ligands. The thermal stabilities were determined in air. When heated they dehydrate to form anhydrous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilities of the complexes were measured over the range 77-300 K and the magnetic moments were calculated. The results reveal the complexes of Ni(II) and Co(II) to be high-spin complexes and that of Cu(II) to form dimer.  相似文献   

16.
The Schiff base ligand, N,N'-bis-(2-thiophenecarboxaldimine)-3,3'-diaminobenzidine (L) obtained from condensation of 2-thiophenecarboxaldehyde and 3,3'-diaminobenzidine, was used to synthesize the complexes of type, [M2L2]Cl4 [M=Co(II), Ni(II), Cu(II), Cd(II) and Hg(II)]. The newly synthesized ligand (L) was characterized on the basis of the results of elemental analysis, FT-IR, 1H NMR, 13C NMR, mass spectroscopic studies and single crystal X-ray crystallography. The characteristic resonance signals in 1H NMR and 13C NMR spectra indicated the presence of azomethine group as a result of condensation reaction. The stoichiometry, bonding and stereochemistries of complexes were ascertained on the basis of results of elemental analysis, magnetic susceptibility measurements, molar conductance and spectroscopic studies viz., FT-IR, 1H and 13C NMR, UV-vis and EPR. EPR, UV-vis and magnetic moment data revealed an octahedral geometry for complexes with distortion in Cu(II) complex and conductivity data show 1:2 electrolytic nature of complexes. Absoption and fluorescence spectroscopic studies supported that Schiff base ligand L and its Co(II), Ni(II) and Cu(II) complexes exhibited significant binding to calf thymus DNA. The complexes exhibited higher affinity to calf thymus DNA than the free Schiff base ligand L.  相似文献   

17.
A series of new transitional metal charge-transfer (CT) complexes with a bipyridinium-based ligand [M(PrBpy)2(SCN)4] (M = Cd(II), Ni(II), Co(II)) and [Cu(PrBpy)(SCN)3(H2O)] (PrBpyCl = N-(2-pyrazinyl)-4,4′-bipyridinium chloride) have been obtained and determined by X-ray diffraction, FT-IR and elemental analysis. The CT absorption bands of the four compounds were observed by diffuse reflection spectroscopy and a photo-induced electron transfer occurs in methanol solution upon light irradiation.  相似文献   

18.
The coordination chemistries of the potential tetradentate ligands N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)ethylenediamine, H4[L1], the unsaturated analogue glyoxal-bis(2-hydroxy-3,5-di-tert-butylanil), H2[L2], and N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2-dimethylpropylenediamine, H4[L3], have been investigated with nickel(II), palladium(II), and copper(II). The complexes prepared and characterized are [Ni(II)(H3L1)2] (1), [Ni(II)(HL2)2].5/8CH2Cl2 (2), [Ni(II)(L3**)] (3), [Pd(II)(L3**)][Pd(II)(H2L3) (4), and [Cu(II)(H2O)(L4)] (5), where (L4)2- is the oxidized diimine form of (L3)4- and (L3**)2- is the bis(o-iminosemiquinonate) diradical form of (L3)4-. The structures of compounds 1-5 have been determined by single crystal X-ray crystallography. In complexes 1 and 2, the ligands (H3L1)- and (HL2)- are tridentate and the nickel ions are in an octahedral ligand environment. The oxidation level of the ligands is that of an aromatic o-aminophenol. 1 and 2 are paramagnetic (mu(eff) approximately 3.2 mu(B) at 300 K), indicating an S = 1 ground state. The diamagnetic, square planar, four-coordinate complexes 3 and [Pd(II)(L3**)] in 4 each contain two antiferromagnetically coupled o-iminobenzosemiquinonate(1-) pi radicals. Diamagnetic [Pd(II)(H2L3)] in 4 forms an eclipsed dimer via four N-H.O hydrogen bonding contacts which yields a nonbonding Pd.Pd contact of 3.0846(4) A. Complex 5 contains a five-coordinate Cu(II) ion and two o-aminophenolate(1-) halves in (L4)2-. The electrochemistries of complexes 3 and 4a ([Pd(II)(L3**)] of 4) have been investigated, and the EPR spectra of the monocations and -anions are reported.  相似文献   

19.
Four novel mixed ligand complexes of Cu(II), Co(II), Ni(II) and Zn(II) with saccharin and nicotinamide were synthesised and characterised on the basis of elemental analysis, FT-IR spectroscopic study, UV–Vis spectrometric and magnetic susceptibility data. The structure of the Cu (II) complex is completely different from those of the Co(II), Ni(II) and Zn(II) complexes. From the frequencies of the saccharinato CO and SO2 modes, it has been proven that the saccharinato ligands in the structure of the Cu complex are coordinated to the metal ion ([Cu(NA)2(Sac)2(H2O)], where NA — nicotinamide, Sac — saccharinato ligand or ion), whilst in the Co(II), Ni(II) and Zn(II) complexes are uncoordinated and exist as ions ([M(NA)2(H2O)4](Sac)2).  相似文献   

20.
l-Tryptophan derived Schiff base ligand and its complexes of the type, [ML(H2O)2]·H2O [M?=?Co(II), Ni(II), Zn(II)] and [CuL] have been synthesized and characterized on the basis of results obtained from elemental analysis, conductivity measurements, ESI-Mass spectral studies, FT-IR, 1H and 13C NMR, UV–Vis spectroscopy and magnetic moment data. The synthesized complexes were subjected to thermogravimetric analysis to study their decomposition pattern and stability. The fluorescence and viscosity measurements reveal that complexes have significant CT-DNA binding. However, upon comparing the DNA binding analyses, Cu(II) complex exhibited significant binding affinity.  相似文献   

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