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1.
Asymmetrical macrocyclic complexes of MnII, CoII, NiII, CuII and ZnII have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X2] (M = MnII, CoII, NiII, CuII and ZnII, L = ligand and X = Cl?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X2] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X2] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X2] complexes exhibit potent broad spectrum antibacterial activity.  相似文献   

2.
The novel (E,E)-dioxime 5,6:13,14-dibenzo-9,10-benzo(15-crown-5)-2,3-bis(hydroxyimino)-7,12-dioxo-1,4,8,11-tetraazacyclotetradecane (H2L) has been synthesized by the reaction of 4′,5′-diaminobenzo(15-crown-5) with N,N′-bis(2-carbomethoxyphenyl)diaminoglyoxime (1). Only mononuclear CoIII and RuII complexes with a metal/ligand ratio of 1:2 have been isolated. The cobalt(III) complex bridged with BF2+ is achieved with H-bonded cobalt(III) complex and borontrifluoride ethyl ether complex. The reaction of BF2 bridged cobalt(III) complex with bis(benzonitril)palladium(II) chloride gives a trinuclear complex. The structures of dioxime and its complexes are proposed according to elemental analyses, 1H and 13C-NMR, IR and mass spectral data.  相似文献   

3.
A new ligand incorporating a dioxime moiety, (2E,3E)-3-[(2-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}phenyl)imino]butan-2-one oxime, (H2Phmdo) (3) has been prepared by reacting 2,3-butanedionemono-{O-[4-(1-methyl-2-oxo-propylideneaminooxy)-2,3-bis-(1-methyl-2-oxo-propylideneaminooxy-methyl)-but-2-enyl]-oxime} (2) with 1,2-phenylenediamine. Mono-, di- and trinuclear copper(II) and/or nickel(II) complexes of H2Phmdo were characterized by elemental analyses, magnetic moments, 1H-n.m.r. and 13C-n.m.r., i.r. and mass spectral studies. The mononuclear copper(II) and nickel(II) complexes of H2Phmdo were found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) or Ni(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The data support the proposed structure of H2Phmdo and its complexes.  相似文献   

4.
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   

5.
Salts containing bis‐phosphonio‐benzophospholide cations 2 a – d with an additional donor site in one of the phosphonio‐moieties were synthesized either via quaternisation of the Ph2P moiety in the neutral phosphonio‐benzophospholide 3 , or via ring‐closure of the functionalized bis‐phosphonium ion 6 . The Ph2P‐substituted cation 2 d formed chelate complexes [M(k2P,P′‐ 2 d )(CO)n]+ with M(CO)n = Ni(CO)2, Fe(CO)3, Cr(CO)4. In the latter case, competition between formation of the chelate and a complex [Cr(kP‐ 2 d )2(CO)4]2+ was observed, and interpreted as a consequence of antagonism between the stabilizing chelate effect and destabilizing ligand–ligand repulsions. The formation of stable PdII and PtII complexes of 2 d suggests that the chelate effect may also overcome the kinetic inhibition which so far prevented isolation of complexes of these metals with bis‐phosphonio‐benzophospholides. The newly synthesized ligands and complexes were characterized by spectroscopic data, and an X‐ray crystal structure analysis of 2 a [Br]. The reactivity of chelate complexes towards Ph3P indicates that the ring phosphorus atom is a weaker donor than the pendant Ph2P‐group.  相似文献   

6.
Summary The synthesis and characterization of some CoII, NiII and CuII complexes with a nitrogen-oxygen donor macrocyclic ligand is reported. Analytical data, i.r. and visible spectra are compatible with an octahedral or distorted octahedral coordination around the metal. For each of the CoL(NCS)2 and NiL(NCS)2 complexes, two crystalline forms were obtained, having different i.r. absorptions for the thiocyanate groups and different x-ray powder diffraction spectra; the pairs of Co-Ni complexes appear to be isostructural.  相似文献   

7.
Cyclam derivatives and their metal complexes have been found to exhibit an anti‐HIV effect and stimulate the activity of stem cells from bone marrow. The strength of their binding to the CXCR4 receptor correlates with anti‐HIV and stem‐cell activities. Knowledge of the conformation and crystal packing of various macrocyclic metal complexes has become important in developing new effective anti‐HIV drugs. The synthesis and preparation of single crystals of a new Cu2+‐doped macrocyclic compound, (3,14‐diethyl‐2,6,13,17‐tetraazatricyclo[16.4.0.07,12]docosane)copper(II) bis(perchlorate)–3,14‐diethyl‐2,13‐diaza‐6,17‐diazoniatricyclo[16.4.0.07,12]docosane bis(perchlorate) (0.69/0.31), {[Cu(C22H44N4)](ClO4)2}0.69·(C22H46N42+·2ClO4?)0.31, is reported. Characterization by X‐ray diffraction analysis shows that the asymmetric unit contains half of a centrosymmetric molecule. The macrocyclic ligand in the compound adopts the most stable trans‐III conformation. The Cu—N distances of 2.015 (3) and 2.047 (3) Å are normal, but the long axial Cu—O bond of 2.795 (3) Å may be due to a combination of the Jahn–Teller effect and the strong in‐plane ligand field. The crystal structure is stabilized by hydrogen bonding between secondary N—H groups, the N atoms of the macrocycle and the O atoms of the perchlorate anions. Hirshfeld surface analysis with 2D (two‐dimensional) fingerprint plots indicates that the main contributions to the crystal packing are from H…H (58.0%) and H…O/O…H (41.9%) interactions. Electron paramagnetic resonance (EPR) properties are also described.  相似文献   

8.
Nine new azodye metal complexes of Mn(II), Co(II), Ni(II), Cu(II), Cr(III), Fe(III), Ru(III), Hf(IV) and Zr(IV) ions have been prepared via the reaction of 5,5′‐((1E,1′E)‐(methylenebis(1,4‐phenylene))bis(diazene‐2,1‐diyl))bis(6‐hydroxy‐2‐thioxo‐2,3‐dihydropyrimidin‐4(5H)‐one) (H4L) with the corresponding metal salts affording sandwich (1 L:1 M), mononuclear (2 L:1 M), binuclear (1 L,2 M) and tetranuclear (1 L,4 M) complexes. Elemental analyses, spectral methods, magnetic moment measurements and thermal studies were utilized to confirm the mode of bonding and geometrical structure for the ligand and its metal complexes. Infrared spectral data show that the H4L ligand chelates with some metal ions in keto–enol–thione or keto–thione manner. It behaves in a neutral/dibasic tetradentate fashion in sandwich and binuclear complexes. Also, it acts as a neutral bidentate moiety in the Cr(III) complex. The spectra reveal that azo group participates in chelation in all complexes. Octahedral geometry was suggested for all chelates but the Cu(II) complex with square planar geometry. The thermal stability and decomposition of the compounds were studied, the data showing that the thermal decomposition ended with metal or metal oxide mixed with carbon as final product. The electron spin resonance spectrum of the Cu(II) complex demonstrates that the free electron is located in the ( ) orbital. Measurements of biological activity against human cell lines Hep‐G2 and MCF‐7 reveal that the Cu(II) complex has a higher cytotoxicity in comparison to the free ligand and other metal complexes, with IC50 values of 6.10 and 5.2 μg ml?1, respectively, while the ligand has anti‐tumour activity relative to some of the investigated metal complexes.  相似文献   

9.
A series of new 24-membered macrocyclic CoII, NiII, CuII and ZnII complexes of the ligands L1H2 and L2H2 were prepared by the non-template and template methods respectively. The ligand L1H2 was formed by the condensation of pyrazole-3,5-dicarbohydrazide and glyoxal and all attempts to isolate the ligand L2H2 were unsuccessful. These, ligand and transition metal complexes were characterized on the basis of elemental analysis, IR, 1HNMR, UV–Visible, magnetic susceptibility measurements, ESR, conductivity measurements, FAB-mass and thermal analysis. The redox behavior of metal ions in the polyazamacrocyclic ligand field is also studied. Electroreduction of carbon dioxide to carbon monoxide is mainly focused on using polydentate azamacrocyclic ligands with amine and imine functionalities, based on the electrochemical behavior of nickel (II) ion in the macrocyclic territory.  相似文献   

10.
The asymmetric unit of {[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}zinc(II) triaqua{μ‐[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}lithium(I)zinc(II) chloride diperchlorate, [Zn(C12H26N5O2)][LiZn(C12H26N5O2)(H2O)3]Cl(ClO4)2, obtained from the reaction between the lithium salt of 4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonane‐1‐acetate and Zn(ClO4)2, contains two ZnII complexes in which each ZnII ion is six‐coordinated by five N‐atom donors and one O‐­atom donor from the ligand. One carboxyl­ate O‐atom donor is not involved in coordination to a ZnII atom, but coordinates to an Li+ ion, the tetrahedral geometry of Li+ being completed by three water mol­ecules. The two complexes are linked via a hydrogen bond between a primary amine N—H group and the carboxyl­ate‐O atom not involved in coordination to a metal.  相似文献   

11.
The Influence of Ring Size on the Structure of Metal Chelates with Tridentate Ligands. IV. Palladium(II) and Platinum(II) Complexes of Pyridyl Substituted Dialkyl Sulfides and Amines [β-(Pyridyl-2)-ethyl]-[(pyridyl-2)-methyl]-amine(2,3-py2tri) forms planar palladium(II) complexes [Pd(2,3-py2tri)X]X (X = Cl, Br) occupying trans-positions as a tridentate ligand. An analogous behaviour is observed with bis[β-(pyridyl-2)-ethyl]-sulfide(3,3-py2Stri) in the chelate compounds [MeII(3,3-py2Stri)X]X (MeII = Pd, Pt; X = Cl, Br, J, SCN). On the other hand the rigid ligand bis[(pyridyl-2)-methyl]-sulfide(2,2-py2Stri) is only bidentate in the complexes MeII(2,2-py2Stri)X2 (MeII = Pd, Pt; X = Cl, Br, J, SCN), one pyridine group does not interact with the central atom. The reasons are the angular relations within the thioether group of 2,2-py2Stri which allow a tridentate coordination in a facial conformation (octahedral and trigonal-bipyramidal nickel(II) and copper(II) complexes), but not in a meridional one (planar palladium(II) and platinum(II) complexes). In Pt(2,2-py2Stri)(SCN)(NCS) one thiocyanato ligand is linked by sulfur, the other one by nitrogen.  相似文献   

12.
Complexes of CrIII, MnII, FeIII, CoII, NiII and CuII containing a macrocyclic pentadentate nitrogen–sulphur donor ligand have been prepared via reaction of a pentadentate ligand (N3S2) with transition metal ions. The N3S2 ligand was prepared by [1 + 1] condensation of 2,6-diacetylpyridine with 1,2-di(o-aminophenylthio(ethane. The structures of the complexes have been elucidated by elemental analyses, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. The complexes are of the high spin type and are six-coordinate.  相似文献   

13.
Coordination compounds of Mn (II), Fe (III), Co (II), Ni (II), Cu (II) and Cd (II) ions were synthesized from reaction with Schiff base ligand 4,6‐bis((E)‐(2‐(pyridin‐2‐yl)ethylidene)amino)pyrimidine‐2‐thiol (HL) derived from the condensation of 4,6‐diaminopyrimidine‐2‐thiol and 2‐(pyridin‐2‐yl)acetaldehyde. Microanalytical data, magnetic susceptibility, infrared and 1H NMR spectroscopies, mass spectrometry, molar conductance, powder X‐ray diffraction and thermal decomposition measurements were used to determine the structure of the prepared complexes. It was found that the coordination between metal ions and bis‐Schiff base ligand was in a molar ratio of 1:1, with formula [M (HL)(H2O)2] Xn (M = Mn (II), Co (II), Ni (II), Cu (II) and Cd (II), n = 2; Fe (III), n = 3). Diffuse reflectance spectra and magnetic susceptibility measurements suggested an octahedral geometry for the complexes. The coordination between bis‐Schiff base ligand and metal ions was through NNNN donor sites in a tetradentate manner. After preparation of the complexes, biological studies were conducted using Gram‐positive (B. subtilis and S. aureus) and Gram‐negative (E. coli and P. aeruginosa) organisms. Metal complexes and ligand displayed acceptable microbial activity against both types of bacteria.  相似文献   

14.
Two new flexible extended dialdehydes (H2hpdd and H2pdd) with different functional pendant arms (? CH2CH2PhOH and ? CH2CH2Ph) have been synthesized and reacted with 1,2‐bis(2‐aminoethoxy)ethane to prepare Schiff‐base macrocyclic complexes in the presence of a ZnII‐ion template. As a result, two preorganized dinuclear ZnII intermediates ( 1 and 2 ), as well as two 42‐membered folded [2+2] macrocyclic dinuclear ZnII complexes ( 3 and 4 ), were produced. The central zinc ions in compounds 1 – 4 showed distinguishable coordination patterns with the dialdehydes and the [2+2] macrocyclic ligands, in which a subtle pH‐adjustment function of the two pendant arms (with or without the phenolic hydroxy group) was believed to play a vital role. Furthermore, cation‐ and anion‐recognition experiments for complexes 3 and 4 revealed that they could selectively recognize acetate ions by the formation of 1:1 stoichiometric complexes, as verified by changes in their UV/Vis and MS (ESI) spectra and even by the naked eye.  相似文献   

15.
Summary Several new complexes of the title ligand (H2MPTS) with CoII, NiII, CuII, and CdII have been prepared. Structural assignments of the complexes have been made based on elemental analysis, molar conductivity, magnetic moment and spectral (i.r.,1H n.m.r., reflectance) studies. The compounds are non-conductors in dimethylsulphoxide. The neutral molecule is coordinated to the metal(II) sulphate as a bidentate ligandvia the two carbonyl groups. The ligand reacts with the metal(II) chlorides with the liberation of two hydrogen ions, behaving as a bianionic quadridentate (NONO) donor. Enolization is confirmed by the pH-titration of H2 MPTS and its metal(II) complexes against NaOH. A distorted octahedral structure is proposed for the CuII complex, while a square planar structure is suggested for both CoII and NiII complexes. The stoichiometry of the complexes formed in EtOH and buffer solutions, their apparent formation constants and the ranges for obedience to Beer's law are reported for CoII, NiII and CuII ions. The ligand pK values are calculated. The antimicrobial activity of H2 MPTS and its CoII, NiII, CuII and MnII complexes is demonstrated.  相似文献   

16.
A family of macrocyclic complexes [M2LnCl2] have been synthesized and characterized (M: CuII or ZnII; Ln: macrocyclic ligand derived from 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and different aliphatic diamines and o-phenylenediamine). The influence of the aromaticity of the ligand and the metal center on the spectroscopic properties of the complexes (absorption and emission) has been studied. Making use of the weak interactions between hydrated potassium ions and the layers of the K0.4Mn0.8PS3 precursor, the obtained macrocyclic complexes have been intercalated in the interlamellar space by a microwave assisted cationic exchange reaction. The optical properties of the obtained hybrid materials are reported. The absorption edge, recorded by solid state reflectance spectroscopy for CuII and the ZnII macrocycle-based composites, is 1.67–1.76 eV, both shifted to lower energy compared with that of the pristine MnPS3.  相似文献   

17.
A novel tetradentate nitrogen donor [N4] macrocyclic ligand, i.e. 1,3,4,8,9,11-hexaaza-2,10-dithia-5,12-dioxo-7,14-diphenyl-cyclotetradecane (L), has been synthesized. Manganese(II),cobalt(II), nickel(II) and copper(II) complexes with this ligand have been prepared and subjected to elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, 1H-n.m.r. (Ligand), i.r., electronic, and e.p.r. spectral studies. On the basis of molar conductance the complexes may be formulated as [M(L)X2] [where M = MnII, CoII, NiII, and CoII,and X = Cl & NO 3 ] due to their nonelectrolytic nature in dimethylformamide (DMF). All the complexes are of the high spin type and are six coordinated. On the basis of i.r., electronic and e.p.r. spectral studies an octahedral geometry has been assigned to MnII, and II, II, complexes, and tetragonal for copper(II) complexes. The antimicrobial activities of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against several species of bacteria and plant pathogenic fungi.  相似文献   

18.
Three photoluminescent complexes containing either ZnII or CdII have been synthesized and their structures determined. Bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)zinc(II), [Zn(C12H10N6)2(C2N3)2], (I), bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(dicyanamido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C2N3)2], (II), and bis[4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole‐κ2N 1,N 5]bis(tricyanomethanido‐κN 1)cadmium(II), [Cd(C12H10N6)2(C4N3)2], (III), all crystallize in the space group P , with the metal centres lying on centres of inversion, but neither analogues (I) and (II) nor CdII complexes (II) and (III) are isomorphous. A combination of N—H…N and C—H…N hydrogen bonds and π–π stacking interactions generates three‐dimensional framework structures in (I) and (II), and a sheet structure in (III). The photoluminescence spectra of (I)–(III) indicate that the energies of the π–π* transitions in the coordinated triazole ligand are modified by minor changes of the ligand geometry associated with coordination to the metal centres.  相似文献   

19.
A new soluble vic-dioxime ligand namely 1,4-bis(2′-hydroxyethyl)-2,3-bis(hydroxyimino)-5,6-diphenylpiperazine, (LH2) containing optically active centers has been prepared as a mixture of isomers from (CNO)2 and N,N-bis(2-hydroxyethyl)stilbendiamine (1) which has been made by the reduction of the condensation of the product of benzaldehyde and 2-aminoethanol in the presence of aluminum amalgam. N,N-coordinated planar metal complexes of this ligand have been synthesized with NiII, CuII, CoII, PdII and UVIO2. Oxidation of (LH)2Co in the presence of a base, such as pyridine, leads to an octahedral complex (LH)2CopyCl containing pyridine and chloride as axial ligands in addition to vic-dioxime ligands. The structures of the ligand and its complexes are proposed on the basis of elemental analysis, 1H-n.m.r., mass, i.r. and u.v.–vis. spectral data. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

20.
Polynuclear complexes are an important class of inorganic functional materials and are of interest particularly for their applications in molecular magnets. Multidentate chelating ligands play an important role in the design and syntheses of polynuclear metal clusters. A novel linear tetranuclear CoII cluster, namely bis{μ3‐(E)‐2‐[(2‐oxidobenzylidene)amino]phenolato}bis{μ2‐(E)‐2‐[(2‐oxidobenzylidene)amino]phenolato}bis(1,10‐phenanthroline)tetracobalt(II), [Co4(C14H11NO2)4(C12H8N2)2], was prepared under solvothermal conditions through a mixed‐ligand synthetic strategy. The structure was determined by X‐ray single‐crystal diffraction and bulk purity was confirmed by powder X‐ray diffraction. The complex molecule has a centrosymmetric tetranuclear chain‐like structure and the four CoII ions are located in two different coordination environments. The CoII ions at the ends of the chain are in a slightly distorted octahedral geometry, while the two inner CoII ions are in five‐coordinate distorted trigonal bipyramidal environments. A magnetic study reveals ferromagnetic CoII…CoII exchange interactions for the complex.  相似文献   

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