首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
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   

2.
A novel quadridentate, N2O2 type Schiff base, synthesized from 1,4‐bis‐(o‐aminophenoxy)butane and 2‐hydroxynaphthalin‐1‐carbaldehyde, forms stable complexes with transition metal ions such as Co(II), Cu(II) and Ni(II) in DMF. Microanalytical data, elemental analysis, magnetic measurements, UV‐visible and IR‐spectra as well as conductance measurements were used to confirm the structures. Electrochemical measurements show that metal complexes undergo quasi‐reversible one‐electron redox processes. The voltammetric results also revealed that the CuL complex has the highest electron transfer rate indicating that both the Cu(II) and Cu(I) forms appear in a similar planar configuration, so the electron transfer does not require larger reorganization of the complex.  相似文献   

3.
By reaction of CuCl2 with H4btc (H4btc = 1,2,4,5‐benzenetetracarboxylic acid) in mixed N,N‐dimethylformamide (DMF) and methanol solution, a new two‐dimensional (2‐D) copper(II) complex [Cu(btc)0.5(DMF)]n ( 1 ) based on the paddlewheel‐like [Cu2(‐CO2)4(DMF)2] building blocks has been synthesized, which is different from those previous Cu‐btc(II) coordination polymers obtained in water medium. Four carboxylate groups of (btc)4? anion in 1 consistently exhibit bidentate bridging coordination mode, affording an unusual coordination mode of (btc)4?. Further analysis indicates C–H···π weak interactions are the primary driving forces to assemble the 2‐D layers of 1 into a 3‐D packing structure.  相似文献   

4.
The Schiff N‐allylamine‐4‐(ethylenediamine‐5‐methylsalicylidene)‐1,8‐naphthalimide (H2L) and its copper(II) complex, [Cu(HL)2] · 0.5DMF, were synthesized and characterized. The crystal structure of the CuII complex reveals a slightly distorted square‐planar arrangement provided by two N and O donors from two deprotonated ligands. In addition, the DNA‐binding properties of the ligand and CuII complex were investigated by fluorescence spectra, electronic absorption, and viscosity measurements. The experimental studies of the DNA‐binding properties indicated that the ligand and CuII complex reacted with DNA via intercalation binding mode, and binding affinity for DNA takes the order: ligand > CuII complex. The antioxidant assay in vitro suggested that both exhibited potential intensely antioxidant properties, and the ligand is more effective than its CuII complex.  相似文献   

5.
The reactions of Co(II) and Cu(II) acetates, valinates, and acetylacetonates with 3,3′,5,5′-tetramethyl-4,4′-dibutyldipyrrolylmethen (HL) in DMF at 298.15 K are studied by spectrophotometric method. The compositions and thermodynamic constants of formation of the Cu(II) and Co(II) complexes are determined using the methods of molar ratios and continuous changes. With an excess in Cu(II) acetate or acetylacetonate, the formation of mixed-ligand complexes CuL(OAc) and CuL(Acac), respectively, was observed, whereas CuL2 complex was detected in the case of HL excess. At either ratio of the reagent concentrations, reactions of Co(II) acetate and acetylacetonate with HL always afforded CoL2 complex, while in the case of Cu(II) and Co(II) valinates, only one amino acid ligand was replaced to give ML(Val) complexes (HVal is valine). The chelating capability of the ligand HL toward the Cu2+ ion was found to be higher than that toward the Co2+ ion.  相似文献   

6.
The azo dye ligand N-diaminomethylene-4-(3-formyl-4-hydroxy-phenylazo)-benzenesulfonamide (HL) and Cu(II), Co(II), and Mn(II) coordination polymers were synthesized in addition to a non-polymeric Pd(II) complex. In all complexes, the ligand bonds to the metal ion through the formyl and α-hydroxy oxygen atoms. The sulfonamide oxygen also coordinates to the metal. The complexes are formulated as [ML2] n , where M?=?Cu(II), Co(II), and Mn(II), and [ML(Cl)(H2O)], where M?=?Pd(II). On the basis of spectral studies and magnetic susceptibility measurements, an octahedral geometry was assigned to Co(II) and Mn(II) complexes, tetragonally elongated octahedral geometry for Cu(II) complex, while the Pd(II) complex was found to be square planar. Crystallization of Cu(II) complex from DMF afforded single crystals of general formula {[Cu(L)2]?·?3DMF} n (2). X-ray structural analysis of 2 revealed that each Cu(II) adopts elongated octahedral geometry affording 1-D chains. The chains are connected by hydrogen bonds, resulting in the formation of 2-D supramolecular assemblies. The crystal structure of HL has also been determined and discussed. Cyclic voltammetric behavior of the ligand and some complexes are also discussed.  相似文献   

7.
A tetra-nuclear, heterometallic copper(II)-cadmium(II) complex, [{CuL(H2O)}2(CuL)Cd](ClO4)2·H2O (1) has been synthesized by reacting the “ligand complex” [CuL] with Cd(ClO4)2 where H2L is the tetradentate di-Schiff base derived from 1,3-propanediamine and 2-hydroxyacetophenone. Complex 1 transforms into a trinuclear species, [(CuL)2Cd(NCS)2] (2) on treatment with an ammonium thiocyanate solution. Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the central Cd(II) ion has a six-coordinate distorted octahedral environment being bonded to six oxygen atoms from three Cu(II) units in 1 and to four oxygen atoms from two [CuL] units along with a couple of thiocyanate nitrogen atoms in complex 2. Complex (1) exhibits reversible reductive (Cu(II)/Cu(I); Epc, −1.03 V) and oxidative (Cu(II)/Cu(III); Epa, +1.04 V, respectively) responses in cyclic voltammetry. The generated Cu(I) species for both the complexes are unstable and undergo disproportionation.  相似文献   

8.
Cu(II) complexes of 14‐membered hexaaza macrocyclic ligand with C‐methyl substituent of the type [CuL](X)2 (where L = 3,10‐bisbenzyl‐6,13‐dimethyl‐1,3,5,8,10,12‐hexaazacyclotetradecane, and X = ClO4, PF6) were synthesized by tandem reaction. They were characterized by spectral and single‐crystal X‐ray diffraction techniques. The complexes show distorted octahedral geometry and the counter ions are weakly coordinated to the metal ion at the axial positions. The macrocyclic ring adopts the trans‐III configuration with six‐ and five‐membered chelate rings in chair and gauche conformation, respectively. It was observed that in the solid state the arrangement of the coordination sphere is distorted octahedral whereas, in solution, a square‐planar structure is predominant. The molar conductance of the complexes indicates that the axially bonded anions are almost dissociated in acetonitrile solution. The Electron Paramagnetic Resonance (EPR) spectrum of complex 1 is axial and consistent with a dx2y2 ground state. The [CuL](ClO4)2 was found to be active against the tested microorganism. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

9.
A new hydrazone (LH2) derived from the condensation of 2‐(4‐fluorobenzamido)benzohydrazide with 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde was used to synthesize Co(III), Ni(II) and Cu(II) complexes. These were characterized using various physicochemical, thermal, spectroscopic and single‐crystal X‐ray diffraction techniques. All the complexes crystallize in a monoclinic crystal system with P21/n space group and Z = 4. Structural studies of [Co(L)(LH)]?H2O indicate the presence of both amido and imidol tautomeric forms of the ligand, resulting in a distorted octahedral geometry around the Co(III) ion. On the other hand, in the [Ni(L)(DMF)] and [Cu(L)(H2O)] complexes, the ligand coordinates to the metal through imidol form resulting in distorted square planar geometry, in which the fourth position is occupied by the oxygen of coordinated DMF in [Ni(L)(DMF)] and by a water molecule in [Cu(L)(H2O)]. Hirshfeld surface calculations were performed to explore hydrogen bonding and C―H???π interactions. Molecular docking studies were carried out to study the interaction between the synthesized compounds and proteins (cyclooxygenase‐2 and 5‐lipoxygenase). The complexes along with the parent ligand were screened for their in vivo anti‐inflammatory activity, using the carrageenan‐induced rat paw oedema method. The complexes show significant anti‐inflammatory potencies.  相似文献   

10.
Reactivity of 3,3′,5,5′-tetramethyl-4,4′dibutyldipyrrolylmethene (HL) in reactions Co(II) and Cu(II) acetates, acetylacetonates, and valinates in DMF (298.15 K) was estimated by spectrophotometric and calorimetric titration methods. The product of the exchange reaction between HL and Co acetate or acetylacetonate was found to be CoL2 complex. With an excess of Cu(II) acetate or acetylacetonate, the reaction resulted in mixed-ligand complexes CuL(AcO) and CuL(Acac), while with an excess of HL, the CuL2 complex was formed. Irrespective of the reagent concentration ratios, the exchange reactions with Cu(II) and Co(II) valinates gave ML(Val) complexes. Thermodynamic parameters of HL reactions with Cu(II) and Co(II) acetates, acetylacetonates, and valinates were determined.  相似文献   

11.
The kinetics of hydrolysis of p‐nitrophenyl picolinate(PNPP) catalyzed by metallomicelles formed from Cu (II), Ni (II) Schiff base complexes (CuL, NiL) and CTAB micelle were investigated in the pH range of 6.0–9.0 at 30°C. For the Cu (II) Schiff base complex CuL, the apparent rate constants (k obsd) of PNPP hydrolysis initially increased with the increasing pH of reaction media, then fell off. For the Ni (II) Schiff base complex NiL, the k obsd always increased with the increasing pH. The kinetic and thermodynamic parameters were calculated. The hydrolysis rate of PNPP catalyzed by Cu (II) complex was much larger than that by Ni (II) complex in CTAB micellar solution. The catalytic mechanism of the PNPP hydrolysis was discussed in detail, and the possibly active specie for the catalytic hydrolysis of PNPP was the monohydroxo metal complex.  相似文献   

12.
A new asymmetric Salamo‐based ligand H2L was synthesized using 3‐tertbutyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H2L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}2], and [{Ni(L)(CH3COO)(CH3CH2OH)}2Ni] with the ligand H2L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H2L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.  相似文献   

13.
Three copper(II) coordination polymers, namely, {[CuL(H2O)2] · 4H2O}n( 1 ), [CuL(H2O)(DMF)]n( 2 ), and [CuL(2, 2′‐bipy)(DMSO)] · DMSO ( 3 ) [H2L = 2, 2′‐(4, 6‐dinitro‐1, 3‐phenyl‐enedioxy)diacetic acid] were synthesized in different solvents (H2O, DMF, and DMSO). X‐ray single crystal diffraction studies show that both complexes 1 and 3 belong to triclinic crystal system and P$\bar{1}$ space group and complex 2 belongs to the monoclinic crystal system and P21/c space group. In three complexes, all the central CuII ions coordinate with the ligand, forming a square pyramidal configuration. Both complexes 1 and 2 show similar 1D chain‐like structure and the chains are further connected by hydrogen bonds, forming 3D frameworks. Complex 3 exhibits a 0D structure due to the introduction of the ligand 2, 2′‐bipy. In addition, the luminescence properties of these complexes were investigated.  相似文献   

14.
Homobinuclear complex (HCuL)2 (1) (H3L: N-3-carboxylsalicylidene-N'-salicylaldehyde-1,2-diaminoethane) was obtained from self-organization of the reported complex HCuL, and its crystal structure was determined through X-ray diffraction at room temperature. The crystal of complex 1 belongs to monolinic system, the space group Cc, a=2.5326(5) nm, b=0.88861(18) nm, c=1.3738(3) nm, β=96.95(3)°, Z=4, R1=0.0520, wR2=0.1185. (HCuL)2 is a dimeric molecule and has extended phenolic oxygen-bridged structure. In addition, using mononuclear complex HCuL as building blocks, Cu(Ⅱ)-Mg(Ⅱ)-Cu(Ⅱ) heterotrinuclear complex 2 was synthesized, and its crystal structure also has been determined by X-ray analysis. The crystal of complex 2 is of monoclinic system, space group Pc, a=1.1816(2) nm, b=1.5599(3) nm, c=1.9642 (4) nm, β=98.22°, Z=2, R1=0.0701, wR2=0.1498. Each dissymmetricai cell unit of complex 2 contains two heterotrinucler neutral molecules: {[CuL(H2O)]Mg[CuL(CH3OH)]} and {[CuL]Mg[CuL(H2O)]}.  相似文献   

15.

In this study, a mononuclear CuL complex was prepared by the use of bis-N,N′-(salicylidene)-1, 3-propanediamine (LH2) and Cu2+ ion. NiCl2 and NiBr2 salt were treated with this complex in dioxanewater medium and two new complexes [(CuL)2NiCl2(H2O)2] and [(CuL)2NiBr2(H2O)2)] with Cu(II)–Ni(II)–Cu(II) nucleus structure were obtained. In addition to this bis-N,N′-(2-hydroxybenzyl)-1,3-diaminopropane (LHH2) was prepared by the reduction of LH2 with NaBH4 in MeOH medium. The treatment of this reduced complex with Cu2+ ion resulted a complex [(CuLH)2CuCl2] with a structure of Cu(II)–Cu(II)–Cu(II). The complexes prepared were characterized by the use of elemental analysis, IR spectroscopy, thermogravimetric and X-ray diffraction methods. The crystal structures of [(CuL)2NiBr2(H2O)2] (СIF file CCDC 1448402) and [(CuLH)2CuCl2] (СIF file CCDC 1448401) complexes were elucidated. It was found that halogen ions are coordinated to terminal Cu2+ ions which are in a distorted square pyramid coordination sphere. It was determined that the central Cu(II), which joins terminal square pyramidal Cu(II), was coordinated only by the phenolic oxygens of the ligand while the central Ni(II) was coordinated by two phenolic oxygens of the organic ligand and two water molecules. These complexes were investigated by XPS and it was found that the terminal and central Cu2+ ions were different in Cu(II)–Cu(II)–Cu(II) complex. Also, the thermal degradation of the CuLH complex unit was observed to exothermic in contrast to the expectations.

  相似文献   

16.
A pair of novel azide‐bridged polynuclear copper(II) complexes, [CuL(μ1,1‐N3)]n ( 1 ) and [Cu4L2(CH3COO)21,1‐N3)4] ( 2 ) (L = 4‐chloro‐2‐[(2‐dimethylaminoethylimino)methyl]phenolate), have been obtained from the same Schiff base ligand and an identical synthetic procedure using anions of the metal salts as the only independent variable. Complex 1 was synthesized using copper(II) nitrate, while complex 2 was synthesized using the copper(II) acetate as the salt. Both of the complexes show novel supramolecular structures in their crystals as elucidated by X‐ray analyses. The polynuclear complex 1 contains [CuL(μ1,1‐N3)]n units as the building blocks, crystallizes in the Pbca space group. The tetra‐nuclear complex 2 contains [Cu4L2(CH3COO)21,1‐N3)4] units as the building blocks, crystallizes in the space group.  相似文献   

17.
Two macrocyclic ligands based on cyclam with trans‐disposed N‐methyl and N‐(4‐aminobenzyl) substituents as well as two methylphosphinic (H2 L1 ) or methylphosphonic (H4 L2 ) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)—K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H4 L2 , probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an “out‐of‐cage” complex and thus accelerate its “in‐cage” binding. The rate of CuII complexation by the phosphinate ligand H2 L1 is comparable to that of cyclam itself and its derivatives with non‐coordinating substituents. Acid‐assisted decomplexation of the copper(II) complexes is relatively fast (τ1/2=44 and 42 s in 1 M aq. HClO4 at 25 °C for H2 L1 and H4 L2 , respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion‐selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non‐carrier‐added 64Cu in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60–70 % recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900‐fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation.  相似文献   

18.
The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin (1) and its Ni (Ⅱ) (2), Cu (Ⅱ) (3), Zn (Ⅱ) (4) complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-(2-Hydroxynaphthyl)-5,10,15,20-tetraphenyl porphyrin (5) and its Ni (Ⅱ) (6), Cu (Ⅱ) (7), Zn (Ⅱ) (8) complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 (70%), 6 (34%), 7 (54%) and 8 (50%), the corresponding 2-(2-naphythoxy)-5, 10,15,20-tetraphenylporphyrin (9), and its Ni (Ⅱ) (10), Cu (Ⅱ) (11), Zn (Ⅱ) (12) complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.  相似文献   

19.
A new potentially octadentate N2O6 Schiff base ligand, H2L derived from the condensation of 2,2′-(1,1′-binaphthyl-2,2′-diylbis(oxy))dianiline and o-vanillin, along with its copper(II) and zinc(II) complexes, is synthesized and has been characterized by elemental analyses, IR, UV–vis, 1H and 13C NMR spectra, as well as conductivity measurements. H2L forms mononuclear complexes of 1:1 (metal:ligand) stoichiometry with Cu(II) and Zn(II), and conductivity data confirm the non-electrolyte nature of these complexes. The [ZnL] and [CuL] complexes display very different solid-state structures, as determined by X-ray crystallography. While the [ZnL] complex has a distorted octahedral geometry about the metal, the [CuL] complex displays a distorted square planar geometry about the copper, with long Cu–O(ether) distances of 2.667 Å.  相似文献   

20.
《中国化学会会志》2017,64(3):261-281
A new Schiff base was prepared from the reaction of 4,4′‐methylenedianiline with 2‐benzoylpyridine in 1:2 molar ratio, as well as its different metal chelates. The structures of the ligand and its metal complexes were studied by elemental analyses, spectroscopic methods (infrared [IR ], ultraviolet–visible [UV –vis], 1H nuclear magnetic resonance [NMR ], electron spin resonance [ESR ]), magnetic moment measurements, and thermal studies. The ligand acts as tetradentate moiety in all complexes. Octahedral geometry was suggested for Mn(II ), Cu(II ), Cr(III ), and Zn(II ) chloride complexes and pentacoordinated structure and square planar geometry for Co(II ), Ni(II ), Cu(NO3 )2, CuBr2 , and Pd(II ) complexes. ESR spectra of copper(II ) complexes ( 4 )–( 6 ) at room temperature display rhombic symmetry for complex ( 4 ) and axial type symmetry for complexes ( 5 ) and ( 6 ), indicating ground state for Cu(II ) complexes. The derivative thermogravimetric (DTG ) curves of the ligand and its metal complexes were analyzed by using the rate equation to calculate the thermodynamic and kinetic parameters, which indicated strong binding of the ligand with the metal ion in some complexes. Also, some of these compounds were screened to establish their potential as anticancer agents against the human hepatic cell line Hep‐G2 . The obtained IC50 value of the copper(II ) bromide complex (4.34 µg/mL ) is the highest among the compounds studied.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号