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1.
Six Schiff-bases HL1-HL4, L5 and L6 [HL1 = 2,6-bis[1-(2-aminoethyl)pyrolidine-iminomethyl]-4-methyl-phenol, HL2 = 2,6-bis[1-(2-aminoethyl)piperidine-iminomethyl]-4-methyl-phenol, HL3 = N-{1-(2-aminoethyl)pyrolidine}salicylideneimine, HL4 = N-{1-(2-aminoethyl)piperidine}salicylideneimine, L5 = 2-benzoyl pyridine-N-{1-(2-aminoethyl)pyrolidine}, L6 = 2-benzoylpyridine-N-{1-(2-aminoethyl)piperidine}] have been synthesized and characterized. Zn(II) complexes of those ligands have been prepared by conventional sequential route as well as by template synthesis. The same complexes are obtained from the two routes as evident from routine physicochemical characterizations. All the Schiff-bases exhibit photoluminescence originating from intraligand (π–π*) transitions. Metal mediated fluorescence enhancement is observed on complexation of HL1-HL4 with Zn(II), whereas metal mediated fluorescence quenching occurs in Zn(II) complexes of L5 and L6.  相似文献   

2.
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   

3.
Nickel(II) complexes of quinoline-2-carbaldehyde N(4),N(4)-(butane-1,4-diyl) thiosemicarbazone (HL1) and 2-benzoylpyridine N(4),N(4)-(butane-1,4-diyl) thiosemicarbazone (HL2) have been synthesized and physico-chemically characterized by means of partial elemental analyses, molar conductance measurements, magnetic measurements, electronic and infrared spectral studies. Three complexes were given the formulae [Ni(HL1)2]Cl2 (1), [Ni(HL2)L2]ClO4 · 7H2O (2) and [NiL2Cl] · 0.5H2O (3). The structure of compound 1 has been solved by single crystal X-ray crystallography and is found to be distorted octahedral. Compound 2, when crystallized in DMSO solution, got deprotonated to form a new compound [Ni(L2)2] (2a), with a distorted octahedral Ni(II) center. In compound 1, HL1 coordinates to the metal in the thione form, while in compounds 2a and 3, HL2 coordinates in its deprotonated thiolate form.  相似文献   

4.
Three new copper(II) complexes [CuL1N3]2 (1), [CuL2N3] (2) and [CuL3N3] (3) with three very similar tridentate Schiff base ligands [HL1?=?6-diethylamino-3-methyl-1-phenyl-4-azahex-3-en-1-one, HL2?=?6-amino-3-methyl-1-phenyl-4-azahex-3-en-1-one and HL3?=?6-amino-3-methyl-1-phenyl-4-azasept-3-en-1-one] have been synthesized and structurally characterized by X-ray crystallography. In complex 1 half of the molecules are basal-apical, end-on azido bridged dimers and the remaining half are square-planar monomers whereas all the molecules in complexes 2 and 3 are monomers with square-planar geometry around Cu(II). A competition between the coordinate bond and H-bond seems to be responsible for the difference in structure of the complexes.  相似文献   

5.
Ten copper(II) complexes {[CuL1Cl] (1), [CuL1NO3]2 (2), [CuL1N3]2 · 2/3H2O (3), [CuL1]2(ClO4)2 · 2H2O (4), [CuL2Cl]2 (5), [CuL2N3] (6), [Cu(HL2)SO4]2 · 4H2O (7), [Cu(HL2)2] (ClO4)2 · 1/2EtOH (8), [CuL3Cl]2 (9), [CuL3NCS] · 1/2H2O (10)} of three NNS donor thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-(methyl), N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of compound 9 has been determined by X-ray diffraction studies and is found that the dimer consists of two square pyramidal Cu(II) centers linked by two chlorine atoms.  相似文献   

6.
Two new pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL1] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL2] have been synthesised by the 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. A Ni(II) complex of HL1 and Co(III) and Fe(III) complexes of HL2 have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N4S2 chromophore around the central metal ion. Each ligand molecule binds the metal ion using the pyrimidyl and azomethine nitrogen and thiolato sulfur atoms (except in the nickel complex, one ligand molecule uses the thione sulfur in lieu of thiolato sulfur atom). In the Ni(II) complex, one of the ligand molecules behaves as a neutral tridentate and the other molecule functions as a uninegative tridentate, whereas in the Co(III) and Fe(III) complexes, the ligand molecules behave as monoanionic tridentate. All the complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from an octahedral geometry of the coordination environment were observed.  相似文献   

7.
Two pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL1] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL2] have been synthesised by 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. One Co(III) and one Mn(II) complex of HL1 and one Mn(II) complex of HL2 have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N4S2 chromophore around the central metal ion. Each ligand molecule binds the metal ion using pyrimidyl nitrogen, azomethine nitrogen and the thiolato sulfur atoms. In the free ligand moieties, the pyrimidine nitrogen atoms, azomethine nitrogen atoms and thione sulfur atoms are in EEE orientation to each other. During chelation, all the donor sites of the ligands are reoriented to ZEZ configuration in order to facilitate the chelation process. In all the complexes, the respective ligand molecule functions as the monoanionic tridentate one. All complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from octahedral geometry of the coordination environment were observed.  相似文献   

8.
Azo Schiff base ligand 2-hydroxy-3-methoxy-5-(tolyldiazenyl)benzaldehyde oxime (HL1) and 2-hydroxy-3-methoxy-5-(methoxyphenyl)benzaldehyde oxime (HL2) were prepared along with their transition metal complexes of Ni(II), Cu(II), and Zn(II). Ligands and their metal complexes were characterized by several analysis techniques. In- vitro antibacterial, antioxidant and anti-inflammatory activities of synthesized ligands and their metal complexes have been studied. Biological study showed that amongst all the synthesized compounds, Cu(II) complexes possessed excellent antibacterial activity than standard antibiotic Chloramphenicol. Ligands (HL1) and (HL2) showed excellent antioxidant as well as anti-inflammatory activity. Both the ligands were tested for their protective effect of free radicals against plasmid DNA and it was found that both the ligands showed good DNA nicking activity.  相似文献   

9.
Three copper(II) Schiff-base complexes, [Cu(L1)(H2O)](ClO4) (1), [Cu(L2)] (2) and [Cu(L3)] (3) have been synthesized and characterized [where HL1 = 1-(N-ortho-hydroxy-acetophenimine)-2-methyl-pyridine], H2L2 = N,N′-(2-hydroxy-propane-1,3-diyl)-bis-salicylideneimine and H2L3 = N,N′-(2,2-dimethyl-propane-1,3-diyl)-bis-salicylideneimine]. The structure of complex 1 has been determined by single crystal X-ray diffraction analysis. In complex 1, the copper(II) ion is coordinated to one oxygen atom and two nitrogen atoms of the tridentate Schiff-base ligand, HL1. The fourth coordination site of the central metal ion is occupied by the oxygen atom from a water molecule. All the complexes exhibit high catalytic activity in the oxidation reactions of a variety of olefins with tert-butyl-hydroperoxide in acetonitrile. The catalytic efficacy of the copper(II) complexes towards olefin oxidation reactions has been studied in different solvent media.  相似文献   

10.
A template synthesis procedure yielded [Ni(HL1)NH3]I, where HL1 is the monoanion of the terdentate ONN benzoylacetone S-methylisothiosemicarbazone ligand. The reaction of this complex with an excess of NH4NCS, pyridine, or hydrazine resulted in the complexes [Ni(HL1)(NH3)NCS] and [Ni(L1)A] (A = Py, N2H4). The monoanionic form of the ligand is obtained by deprotonation of the enolic form of the benzoylacetone moiety, whereas the dianion is formed by additional deprotonation of the terminal NH2 group. Finally, the reaction of [Ni(HL1)NH3]I with salicyladehyde produced the NiL2 complex in which L2 stands for the dianion of the ONNO ligand N(1)-2-butylidene-4-oxo-4-phenyl-N(4)-salicylidene-S-methylisothiosemicarbazide. All complexes are diamagnetic and have a square-planar configuration, except for [Ni(HL1)(NH3)NCS], for which te data of i.r. spectra suggest a square-pyramidal structure. The electronic absorption spectra of the ethanolic solutions of all complexes are characteristic of typical square-planar coordination of nickel(II).  相似文献   

11.
Nine complexes of copper(II), cobalt(II), Ni(II), and Zn(II) chlorides with naphtho[1,2,-c][1,2,5]oxadiazol-9-ol (HL1), naphtho[1,2-c][1,2,5]thiadiazol-9-ol (HL2), and naphtho[1,2-c][1,2,5]selenadiazol-9-ol (HL3) have been synthesized, isolated in the crystalline state, and studied by physicochemical methods. The composition of the complexes in solutions as been determined and their stability constants have been calculated from spectrophotometric data. The electronic structures of the ligands and complexes have been calculated by quantum-chemical methods. The crystal and molecular structure of HL2 has been determined by X-ray crystallography.  相似文献   

12.
Metal-ion complexation of 7-benzylimidazo[1,2-a]pyrazin-3(7H)-one derivative (2) with Li+, Mg2+, Ca2+, Ba2+, Sc3+, and La3+ in acetonitrile resulted in successive modulations of its UV/vis absorption and fluorescence spectroscopic properties. This result indicates that 2 can be used as a colorimetric and fluorometric sensor of the Lewis acidity of a metal ion in aprotic solutions. The hypothesis that the metal-ion complex has a O10(imidazopyrazinone)-metal ion bond was supported by X-ray crystallographic analysis and quantum chemical calculations for a Li+ complex of 7-methylimidazo[1,2-a]pyrazin-3(7H)-one derivative (1).  相似文献   

13.
Seven Zn(II) and Cd(II) complexes of ON donor acetone-N(4)-phenylsemicarbazone (HL) have been synthesized and physico-chemically characterized by partial elemental analyses, molar conductance measurements, infrared, electronic and 1H NMR spectral studies. The semicarbazone binds the metal as a neutral bidentate ligand in all the complexes. The crystal structures of acetone-N(4)-phenylsemicarbazone and [Cd(HL)2Cl2] have been determined by X-ray diffraction studies. The coordination geometry around cadmium(II) in the complex [Cd(HL)2Cl2] is distorted octahedral.  相似文献   

14.
Reactions of the ruthenium complexes [RuH(CO)Cl(PPh3)3] and [RuCl2(PPh3)3] with hetero-difunctional S,N-donor ligands 2-mercapto-5-methyl-1,3,5-thiadiazole (HL1), 2-mercapto-4-methyl-5-thiazoleacetic acid (HL2), and 2-mercaptobenzothiazole (HL3) have been investigated. Neutral complexes [RuCl(CO)(PPh3)2(HL1)] (1), [RuCl(CO)(PPh3)2(HL2)] (2), [RuCl(CO)(PPh3)2(HL3)] (3), [Ru(PPh3)2(HL1)2] (4), [RuCl(PPh3)3(HL2)] (5), and [RuCl(PPh3)3(HL3)] (6) imparting κ2-S,N-bonded ligands have been isolated from these reactions. Complexes 1 and 4 reacted with diphenyl-2-pyridylphosphine (PPh2Py) to give neutral κ1-P bonded complexes [RuCl(CO)(κ1-P-PPh2Py)2(HL1)] (7), and [Ru(κ1-P-PPh2Py)2(HL1)2] (8). Complexes 1-8 have been characterized by analytical, spectral (IR, NMR, and electronic absorption) and electrochemical studies. Molecular structures of 1, 2, 4, and 7 have been determined crystallographically. Crystal structure determination revealed coordination of the mercapto-thiadiazole ligands (HL1-HL3) to ruthenium as κ2-N,S-thiolates and presence of rare intermolecular S-S weak bonding interaction in complex 1.  相似文献   

15.
Schiff base ligands HL1–HL6 have been prepared from the reaction of 2,6-diformyl-4-t-butylphenol and 2,6-di-formyl-4-methylphenol with various aromatic amines in ethanolic solution. The Schiff base ligands 2,2′-dipyridine (dp) mixed-ligand CuII complexes have been obtained. Mixed-ligand CuII complexes containing the dp ligand have ionic nature and they conduct the electricity in solution media. The complexes have been obtained in two different forms: one of them is [Cu2(Ln)Cl3] (n: 1, 2, 3, 4, 5 and 6) and other complexes have the general formula [Cu2(Ln)(dp)2]3Cl. Ligands and their complexes have been characterized by elemental analyses, FT-IR, electronic spectra, molar conductance, 1H(13C)-n.m.r. and mass spectral data. Their stoichiometric protonation constants have been determined potentiometrically in dioxan using a combined pH electrode at 25 °C, under a nitrogen atmosphere. For the calculation of the protonation constants, PKAS computer programme has been used. The effects of the substituents on the protonation constants and the additivities of these effects are discussed. The antimicrobial activity studies of the ligands and their complexes have been studied against the Bacillus megaterium, Micrococcus luteus, Corynebavterium xenosis, Enterococcuc faecalis, bacteria and Saccoramyces cerevisia, yeast. The catalytic properties of the complexes have been studied on the ascorbic acid, catechol and 2,6-di-t-butylphenol substrates. Thermal behaviour of the complexes has been studied by thermal techniques.  相似文献   

16.
The reactions of palladium(II) salts with 2-mercaptobenzimidazole (HL) and its 5,6-difluorinated derivative (HLF) were investigated. In the presence of hydrochloric acid, PdCl2 and K2PdCl4 react with HL and HLF in the ethanol—water and acetonitrile—water systems to form the mono-nuclear dicationic complexes [Pd(HL)4]Cl2 (1) and [Pd(LF)4]Cl2 (2). In the absence of HCl, the reactions afford the tetranuclear complex Pd4[(L)23-S,N-(L))2S,N-(L))4] (3). The reaction of triethylamine with an ethanolic solution of 3 leads to degradation of 3 and the formation of the lantern-type dinuclear complex Pd2[(μ2-(L)4] (4), in which the palladium atoms are in the nonequivalent coordination environment, PdN4 and PdS4. The reaction of K2PdCl4 with HL or HLF in the THF—water or acetonitrile—water systems (for the reaction with HLF) in the presence of Et3N produces the lantern-type dinuclear complexes Pd2[(μS,N′-(L3))4] and Pd2[(μ-S,N′-(LF))4] (5), in which the metal atoms are in the equivalent coordination environment (cis-PdN2S2). Dedicated to Academician G. A. Tolstikov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 45–52, January, 2008.  相似文献   

17.
Anodic oxidation of cobalt and copper metals in an anhydrous acetone solution of pyridine-2-(1H)-thione-3-cyano-4-(2-bromophenyl)-5,6-ring fused cycloheptane (HL1) and its derivatives, (HL2), (HL3), (HL4), (HL5), (HL6), (HL7), (HL8), and (HL9) yields complexes of composition [M(L)2·(H2O)2]·n H2O and [M(L)2·(acetone)2], where M = Co(II) or Cu(II) and L is the ligand. Also, reaction of an aqueous ethanolic solution of Co(Ac)2·2H2O with the previous ligands was prepared. Elemental analysis, and infrared and electronic spectral data are presented to confirm the formulation of the amorphous complexes. The spectral data indicate that the ligands are coordinated to the metal via the thioenol sulfur atom and the nitrogen atom of cyano groups. The ligands reacts in the enol form through the anodic dissolution of the ligands or during the reaction with metal salts. The ligand field parameters and crystal field splitting energies, Δo, for different cobalt metal complexes were calculated.  相似文献   

18.
Four dinuclear cadmium(II) complexes, [Cd2(L1)(μ2-Cl)Cl2] (1), [Cd2(L2)(μ2-Cl)Cl2] (2), [Cd2(L3)(μ2-Cl)Cl2] (3), and [Cd2(L4)3ClO4] (4), where HL1 = 4-methyl-2,6-bis(1-(2-piperidinoethyl)iminomethyl)-phenol, HL2 = 4-methyl-2,6-bis(1-(2-pyrrolidinoethyl)iminomethyl)-phenol, HL3 = 4-methyl-2,6-bis(1-(2-morpholinoethyl)iminomethyl)-phenol and HL4 = 4-methyl-2,6-bis(cyclohexylmethyl)iminomethyl)-phenol, were synthesized. They were characterized by elemental analysis, FT-IR, UV–Vis, fluorescence and electronspray ionization mass spectroscopy. Complexes 1 and 4 were also characterized by single crystal X-ray analysis. The cadmiums atoms in 1 are linked by μ2-chloride in a distorted square pyramidal geometry, whereas cadmium atom in 4 is in a distorted octahedral environment. The complexes show emission bands around 500 nm with excitation at 395 nm.  相似文献   

19.
The synthesis and characterization of new transition metal complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 3‐(2‐hydroxynaph‐1‐ylazo)‐1,2,4‐triazole ( HL1 ) and 3‐(2‐hydroxy‐3‐carboxynaph‐1‐ylazo)‐1,2,4‐triazole ( HL2 ) have been carried out. Their structures were confirmed by elemental analyses, thermal analyses, spectral and magnetic data. The IR and 1H NMR spectra indicated that HL1 and HL2 coordinated to the metal ions as bidentate monobasic ligands via the hydroxyl O and azo N atoms. The UV‐Vis, ESR spectra and magnetic moment data revealed the formation of octahedral complexes [Mn L1 (AcO)(H2O)3] ( 1 ), [Co L1 (AcO)(H2O)3]·H2O ( 2 ), [Mn L2 (AcO)(H2O)3] ( 6 ) and [Co L2 (AcO)(H2O)3] ( 7 ), [Ni L1 (AcO)(H2O)] ( 3 ), [Zn L1 (AcO)(H2O)]·H2O ( 5 ), [Ni L2 (AcO)(H2O)] ( 8 ), [Zn L2 (AcO)(H2O)]·10H2O ( 10 ) have tetrahedral geometry, whereas [Cu L1 (AcO)(H2O)2] ( 4 ) and [Cu L2 (AcO)(H2O)2]·5H2O ( 9 ) have square pyramidal geometry.. The mass spectra of the complexes under EI‐con‐ ditions showed the highest peaks corresponding to their molecular weights, based on the atomic weights of 55Mn, 59Co, 58Ni, 63Cu and 64Zn isotopes; besides, other peaks containing other isotopes distribution of the metal. Kinetic and thermodynamic parameters of the thermal decomposition stages were computed from the thermal data using Coats‐Redfern method. HL2 and complexes 6 – 10 were found to have moderate antimicrobial activities against Staphylococcus aureus (gram positive), Escherichia coli (gram negative) and Salmonella sp bacteria, and antifungal activity against Fusarium oxysporum, Aspergillus niger and Candida albicans. Also, in most cases, metallation increased the activity compared with the free ligand.  相似文献   

20.
《印度化学会志》2021,98(10):100168
The three new Cobalt(II) complexes [Co(L1)2(H2O)2] (1), [Co(L2)2(H2O)2] (2), and [Co(L3)2(H2O)2] (3) have been synthesized by interaction of acyl pyrazolone ligands, 4-(4-chlorobenzoyl)3-methyl1-phenyl1H-pyrazole5(4H)-one (HL1), 4-(4-chlorobenzoyl)1-(3-chlorophenyl)3-methyl1H-pyrazole5(4H)-one (HL2) and 5-methyl4-(4-methylbenzoyl)2-phenyl2,4-dihydro3H-pyrazole3-one (HL3) with CoCl2.6H2O. The complexes were screened using FTIR, UV–Vis, TGA, and Single Crystal X-ray diffraction spectroscopic techniques. A relative study of the ligands’ FTIR spectra and their metal complexes reveal the formation, sifting, and disappearance of several bands during complexation. Other interpretations stipulated that these three complexes are mononuclear and exhibited octahedral geometry around Co2+.Triclinic crystal system, Distortion in Octahedral geometry, and Intermolecular hydrogen bonding confirmed by Single-crystal XRD analysis of [Co(L3)2(EtOH)2] complex.  相似文献   

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