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1.
The Cu(II) and Co(II) complexes with 3,5-diphenyl-4-amino-1,2,4-triazole (L) of the composition CuLA2 · H2O (A = Cl?, Br?), CuL2A2 (A = Cl?, Br?, NO 3 ? ), CoL2A2 · nH2O (A = Cl?, n = 1; A = NCS?, n = 0) are synthesized. In these complexes, the ligand L is coordinated to a metal in monodentate mode through the heterocyclic N(1) atom. The Cu: L = 1: 1 complexes have binuclear structures with the anions acting as bridges, whereas the M: L = 1: 2 complexes are mononuclear. Both ferro-and antiferromagnetic exchange interactions are detected for the synthesized complexes.  相似文献   

2.
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   

3.
A series of binuclear Co(II), Ni(II) and Cu(II) complexes were synthesized by the template condensation of glyoxal, biacetyl or benzil bis-hydrazide, 2,6-diformyl-4-methylphenol and Co(II), Ni(II) or Cu(II) chloride in a 2:2:2 M ratio in ethanol. These 22-membered macrocyclic complexes were characterized by elemental analyses, magnetic, molar conductance, spectral, thermal and fluorescence studies. Elemental analyses suggest the complexes have a 2:1 stoichiometry of the type [M2LX2nH2O and [Ni2LX22H2O]·nH2O (where M = Co(II) and Cu(II); L = H2L1, H2L2 and H2L3; X = Cl; n = 2). From the spectroscopic and magnetic studies, it has been concluded that the Co(II) and Cu(II) complexes display a five coordinated square pyramidal geometry and the Ni(II) complexes have a six coordinated octahedral geometry. The Schiff bases and their metal complexes have also been screened for their antibacterial and antifungal activities by the MIC method.  相似文献   

4.
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   

5.
Copper(II) salts were reacted with various quinoline aldehyde chalcogensemicarbazones to yield compounds formulated as Cu(HL)X2 · nH2O (I: HL = quinoline aldehyde thiosemicarbazone (HL1), X = ClO4, n = 2; II: HL = quinoline aldehyde 4-C2H5-thiosemicarbazone (HL1a), X = NO3, n = 0; III: HL = quinoline aldehyde semicarbazone (HL2), X = ClO4, n = 3 and IV: HL = quinoline aldehyde 4-Ph-semicarbazone (HL2a), X = NO3, n = 1). Regardless of the reagent ratio, the products were compounds having the metal: ligand ratio of 1: 1, where the organic ligand was coordinated tridentate in a molecular form. Single-crystal X-ray diffraction showed that, depending on the chalcogen atom in the organic ligand (S or O), the substituent in the 4th position (at the terminal nitrogen atom), and the specifics of the acido ligand, complexes I–IV had appreciably differing molecular structure organizations. The structures of I and III are formed by a 1D charged coordination polymer, ClO 4 ? anions, and water molecules and may be described by the formula [Cu(HL)(H2O)(ClO4)] n (ClO4) n · nH2O. Copper(II) coordination polyhedra in I and II are (4 + 2) and (4 + 1 + 1) tetragonal bipyramids, respectively. In II and IV, the structures are monomeric and can be described as [Cu(HL1a)(NO3)2] with the metal coordination polyhedron shaped as a (4 + 1) tetragonal pyramid in II and as [Cu(HL2a)(H2O)(NO3)](NO3) with the metal coordination polyhedron shaped as a (3 + 2) trigonal bipyramid in IV. The structure of II is built of molecular complexes, each comprising, apart from ligand HL1a, two monodentate coordinated NO 3 ? groups. The oxygen atom of one anion together with the NNS donor atom set of ligand HL1a form the base, and the oxygen atom of the other anion is in the apex of the coordination polyhedron. In IV, the structure is ionic and built of NO 3 ? anions and [Cu(HL2a)(H2O)(NO3)]+ complex cations, where a cationic coordination polyhedron has a trigonal-bipyramidal configuration with organic ligand HL2a positioned along the long edge. The bipyramidal base is made up by the oxygen atoms of the coordinated water molecule and monodentate nitrato group and the nitrogen atom N2 of the azomethyne group.  相似文献   

6.
ILHAN  Salih TEMEL  Hamdi KILIC  Ahmet 《中国化学》2007,25(10):1547-1550
Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis(2-formylphenoxy)butane with diamines and Cu(NO3)2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu(Ⅱ) complexes were found to be 1 : 1. The Cu(Ⅱ) complexes are 1 : 2 electrolytes as shown by their molar conductivities (∧m) in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu(Ⅱ) complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.  相似文献   

7.
The synthesis, spectroscopic, and magnetic characterization of two new copper(II) and cobalt(II) complexes are described. Both two compounds have the general formula [M(L)2(Cl)2] (M = Cu (I), Co (II); L = 2-amino-5-bromopyridine). These complexes were prepared in one-step synthesis and characterized by elemental analysis, FT-IR, UV-Vis, and EPR spectroscopy. Moreover, the single crystal structure of complex I was studied by the X-ray diffraction method. This compound consists of mononuclear units consisting of two ligands linked to metal via the nitrogen of pyridine ring. The UV-Vis spectra of copper(II) and cobalt(II) complexes show three and five absorption bands, respectively, attributed to the d-d transition of the metal ion, ligand → metal charge transfer and π → π* or n → π* transitions of the ligand. The FT-IR spectra show MN2Cl2 vibrations at 500–300 cm?1. The complexes show room temperature magnetic moments of 1.78 and 4.12 μB for Cu(II) and Co(II), respectively. The X-band electron spin resonance (ESR) spectra of Cu(II) complex in DMF or DMSO frozen at liquid nitrogen temperature show the typical ΔMS = ±1 transition.  相似文献   

8.
Novel zinc(II), copper(II), and cobalt(II) complexes of the Schiff base derived from 2‐hydroxy‐1‐naphthaldehyde and D, L ‐selenomethionine were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and powder XRD. The analytical data showed the composition of the metal complex to be ML(H2O), where L is the Schiff base ligand and M = Co(II), Cu(II) and Zn(II). IR results confirmed the tridentate binding of the Schiff base ligand involving azomethine nitrogen, naphthol oxygen and carboxylato oxygen atoms. 1H NMR spectral data of lithium salt of the Schiff base ligand [Li(HL)] and ZnL(H2O) agreed with the proposed structures. The conductivity values of complexes between 12.50 and 15.45 S cm2 mol?1 in DMF suggested the presence of non‐electrolyte species. The powder XRD studies indicated that Co(II) complex is amorphous, whereas Cu(II) and Zn(II) complexes are crystalline. The results of antibacterial and antifungal screening studies indicated that Li(HL) and its metal complexes are active, but CuL(H2O) is most active among them. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

9.
A series of compounds of the general formula Cu(HL)X2 · nH2O (compound I, X = ClO4, n = 3; compound II, X = NO3, n = 2; compound III, X = Cl, n = 0.5; compound IV, X = 1/2SO4, n = 0) is isolated by the reactions of the copper(II) salts with quinolinaldehyde semicarbazone (HL). Regardless of the reactant ratio, only the compounds with a metal to ligand mole ratio of 1: 1 are formed, where the organic reactant is coordinated in the molecular form. The X-ray diffraction analyses of the [Cu(HL)(NO3)(H2O)](NO3) · H2O (II) and [Cu(HL)Cl2] · 0.5H2O(III) compounds show their substantially different organizations of the molecular structures depending on the specifics of the acido ligand. An ionic structure with one NO 3 ? anion incorporated into the inner coordination sphere of the metal as a bidentate chelate ligand is observed in compound II. Molecular tetragonal pyramidal complexes associated into a dimer due to the bridging function of one coordinated Cl? anion are formed in structure III. The coordination polyhedron of the copper atom in structures II and III is an asymmetrically extended tetragonal bipyramid. The CuClCu angle equal to 90° and the distance between two planes in compound III equal to 2.978 Å determine the insignificant antiferromagnetic interaction in this compound (g = 2.1, J = ?2.5 cm?1).  相似文献   

10.
B3LYP/6-31++G(d,p) optimizations on models for the metal cyanin, Cy, complexes [MCy(H2O) n ]+, (M = Zn(II), Cu(II); n = 2, 3, 4) in aqueous solution indicate that 4 is the most favoured coordination number in both cases. SP -4 and T -4 geometries are nearly isoenergetic for the former, while SP -4 is the only one obtained for the latter. Anionic cyanin displays higher affinity for Cu(II) than for Zn(II) or Mg(II). The electron density reorganization of cyanin model accompanying the complexation process was analyzed by means of the quantum theory of atoms in molecules. This analysis reveals that: (1) the O4′–M bond is stronger than O3′–M; (2) anionic cyanin displays a dual character between 4′-keto-quinoidal and 3′,4′-dienolate resonance forms; (3) Cu(II) takes more electron density than Zn(II) from Cy? and water ligands; (4) when the coordination number increases, each ligand (Cy? or water) transfers less electron density; (5) complex formation modifies the electron density in all the atoms of the ligands, but the largest modifications are displayed within the AC bicycle of Cy?; and (6) a third part of density lost by the Cy? ligand is removed from hydrogens.  相似文献   

11.
Acetoxyalkyl metal derivatives M(C5H5)(CO)n[CHROC(O)Me] [M = Fe, n = 2; M = Mo, n = 3; R = H, Me] are readily prepared by reaction of bromoalkylacetates with the appropriate cyclopentadienylcarbonylmetallate anion. The complexes are characterised by their NMR (1H and 13C) and IR parameters and by mass spectrometry. The acetoxyethyl species are thermally labile via β-hydrogen transfer. Treatment of acetoxymethyl complexes with protic acids leads to carbon-oxygen cleavage and release of acetic acid; HCl affords chloromethyl complexes, carboxylic acids yield new carboxylatomethyl derivatives, HBF4 leads to decomposition. The metalloesters are resistant to hydrolysis, transesterification and carboxylate displacement by nucleophiles (HO?, MeO?, H2N? Et2N?). Migratory insertion of CO could not be induced.  相似文献   

12.
Novel complexes of type M2LCl4·nH2O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV–vis, 1H NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells.  相似文献   

13.
Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates were investigated and their composition, solubility in water at 295 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with molar ratio of metal to organic ligand of 1.0:1.0 and general formula: M [ CH3C6H3(CO2)2nH2o (n=1-3) were recorded and their decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Mn, Co, Ni, Zn, Cd) or two steps (Cu) and next the anhydrous complexes decompose to oxides directly (Cu, Zn), with intermediate formation of carbonates (Mn, Cd), oxocarbonates (Ni) or carbonate and free metal (Co). The carboxylate groups in the complexes studied are mono- and bidentate (Co, Ni), bidentate chelating and bridging (Zn) or bidentate chelating (Mn, Cu, Cd). The magnetic moments for paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.92, 5.05, 3.36 and 1.96 M.B., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

14.
A new calix[4]pyrrole functionalized vic-dioxime, 3-(4-methyl-9,9,14,14,19,19-hexaethylcalix[4]pyrrole)benzoaminoglyoxime (LH2) was synthesized from anti-chloroglyoxime and 3-aminophenyl-calix[4]pyrrole at room temperature. The mononuclear complexes {nickel(II), copper(II) and cobalt(II)} of this vic-dioxime ligand were prepared and their structures were confirmed by elemental analysis, IR and UV–Vis spectrophotometry, magnetic susceptibility; the MS, 1H and 13C NMR spectra of the LH2 ligand and its Ni(II) complex were also recorded. The experimental results indicated that the ligand:metal ratio was 2:1 in the cases of Ni(II), Cu(II) and Co(II) complexes as is with most vic-dioximes. Electrochemical properties of the ligand, and its complexes were investigated in DMSO solution by cyclic voltammetry at 200?mV?s?1 scan rate.  相似文献   

15.
New cobalt(II), copper(II) and zinc(II) complexes of Schiff base derived from D,L ‐selenomethionine and salicylaldehyde were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and biological activity. The analytical data showed that the Schiff base ligand acts as tridentate towards divalent metal ions (cobalt, copper, zinc) via the azomethine‐N, carboxylate oxygen and phenolato oxygen by a stoichiometric reaction of M:L (1:1) to form metal complexes [ML(H2O)], where L is the Schiff base ligand derived from D,L ‐selenomethionine and salicylaldehyde and M = Co(II), Cu(II) and Zn(II). 1H NMR spectral data of the ligand and Zn(II) complex agree with proposed structures. The conductivity values between 12.87 and 15.63 S cm2 mol?1 in DMF imply the presence of non‐electrolyte species. Antibacterial and antifungal results indicate that the metal complexes are more active than the ligand. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

16.
Abstract

Four new Schiff-base ligands have been prepared from the condensation of 3-formyl-4-hy-droxy-1,8-naphthyridin-2-one with different diamines and a triamine, H2La-H2Ld. Two series of Ni(II) and Cu(II) complexes with the four ligands were also prepared. The ligands and their metal complexes were characterized by chemical analyses, IR, Far-IR, electronic, ESR and mass spectra as well as magnetic measurements and X-ray diffraction patterns.

Different products for Ni(II) and Cu(II) were obtained in similar reactions with the same metal salt, depending on the nature of the ligand. Different geometries were also obtained depending on the counter anion of metal salt. Thus, violet square-planar Cu(II) complexes were obtained with Cu(OAc)2. H2O and green octahedral ones with CuCl2. 2H2O, except the reaction with ligand H2Ld which gave only an octahedral product whether the anion was acetate, chloride or perchlorate. Electronic and ESR spectra were used to differentiate between the two geometries of the Cu(II) complexes. The green octahedral Cu(II) complexes undergo irreversible thermochromism to the violet square-planar complexes except the copper complex of the ligand H2Ld which did not not show any color change and retained its octahedral geometry. Based on the magnetic moments and thermal analyses, only one Ni(II) complex of the Schiffbase ligand H2Lc undergoes reversible thermochromism from green (octahedral) to red (squareplanar). The reverse change of the thermal product (red) to the parent complex (green) proceeded on exposure to atmospheric air for a few minutes. On the other hand, Ni(II) complexes of ligands H2La and H2Lb have stable square-planar geometry and all efforts to add other ligands such as H2O or pyridine to these complexes failed to yield other products. The corresponding Cu(II) complexes were easily transformed to their octahedral geometry by adding H2O or pyridine and heating.  相似文献   

17.
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   

18.
Four new mixed ligand complexes were prepared by the reaction of title metal dichloroacetates and 2,4'-bipyridine. The general formulae of synthesized compounds are M(2,4'-bpy)2(CCl2HCOO)2·nH2O (where M(II)=Mn, Co, Ni, Cu; 2,4'-bpy=2,4'-bipyridine, n=2 or 4). The complexes have been isolated from aqueous media and characterized by chemical analysis, molar conductance (in MeOH, DMSO and DMF), magnetic, IR and VIS spectral studies. The nature of metal(II)-ligand coordination is discussed. The thermal behaviour of obtained complexes was studied by thermal analysis and TG-MS techniques in air. IR, X-ray powder diffraction and thermoanalytical data were used for the determination of solid intermediate products of the thermal decomposition. The principal volatile products of thermal decomposition of complexes were proved by mass spectroscopy: H2O+, CO+ 2, HCl+ 2, Cl+ 2, NO+ and other. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

19.
New copper (II) complexes of Schiff bases with 1,2-di(imino-2-aminomethylpyridil)ethane with the general composition CuLX m (H2O) x , [L = Schiff base, X = Cl?, Br?, NO3 ?, ClO4 ?, CH3COO?, m = 2; X = SO4 2?, m = 1] were prepared by template synthesis. The complexes were characterized by elemental analysis, conductivity measurements, magnetic moments, IR, UV–VIS and EPR spectra. The thermal behavior of complexes was studied using thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). Infrared spectra of all complexes are in good agreement with the coordination of a neutral tetradentate N4 ligand to the cooper (II) through azomethinic and pyridinic nitrogen. Magnetic, EPR and electronic spectral studies show a monomeric distorted octahedral geometry for all Cu(II) complexes. Conductance measurements suggest the non-electrolytic nature of the compounds, except for copper (II) nitrate and perchlorate complexes which are 1:2 electrolytes. Heats of decomposition, ΔH, associated with the exothermal effects were also determined.  相似文献   

20.
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   

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