The synthesis of four rhodium(II) paddlewheel complexes bearing axial aromatic amines and coumarin ligands, with formula [Rh2(OAc)4(L)2] (L = NH2Mesityl (1), NH2Dip (2), NH2Couma (3), coumarin (4)), prompted by microwave irradiation, was carried out successfully. All of the complexes were characterized by the melting point, elemental analysis, NMR, IR, and UV/Visible spectroscopy. Additionally, the structure of complexes 1-2 and 4 was corroborated by single-crystal X-ray diffraction. Cyclic voltammetry, ESI-MS, and tandem MS analyses were carried out in compound 1 for gaining further insight into its stability. Finally, a DFT study shows that complexes 1–4 are the thermodynamic products, having as intermediates complexes 1′–4′ which, under our experimental conditions, cannot be isolated.
The titled Zn(II) complex was synthesized by reacting the compound (E) -2-hydroxy- N ′-{1-(4-methoxyphenyl)ethylidene}benzohydrazide with zinc(II) acetate dihydrate in alkaline DMSO and ethanol solution under reflux condition for 28 hours. The resulting solid was filtered and recrystallized from the mixture of ethanol and DMSO. The hydrazone Schiff base and its Zn(II) complex were characterized using 1 H, 13 C NMR, FTIR, UV-Vis spectroscopy, and single crystal X-ray diffraction analysis. Meanwhile, their antibacterial activities were examined using disc diffusion method. The spectral studies showed that the hydrazone Schiff base underwent keto-enol tautomerization, forming a bidentate ligand (N,O) towards Zn(II) ion. Surprisingly, on top of the two hydrazone Schiff base molecules which coordinated to the Zn metal center, an additional DMSO molecule was found attached to the Zn metal center in the crystal data, resulting in a 5-coordinate distorted trigonal bipyramidal Zn(II) complex. Both hydrazone Schiff base and its Zn(II) complexes were found to exhibit low antibacterial activity even when the concentrations were increased to 800 ppm.
The present paper reports the use of 31 P NMR spectroscopy to predict the isomer structures of [bis{4-methoxy-phenyl-[3-(4-methoxy-phenyl)-allylidene]-amino}]-bis[triphenylphosphine]ruthenium(II), also known as bis{(di- p -anisole)-1,4-azabutadiene}-bis[triphenylphosphine]ruthenium(II), complexes. The complexation reaction was carried out under refluxing condition of (di- p -anisole)-1,4-azabutadiene (compound 1 ), triphenylphosphine (PPh 3 ), and ruthenium chloride in the ratio of 2 : 2 : 1 for five hours. In addition, ruthenium(II) complexes were also characterized using FTIR and UV-Vis spectroscopy to support the formation of ruthenium(II) complexes. 31 P NMR spectroscopic study on ruthenium(II) complexes suggested that there are three isomers present after the complexation reaction and all the ruthenium complexes demonstrate octahedral geometry.
We report the synthesis of a new asymmetric azacryptand (L1), characterized by three p-xylyl spacers, one of which carries a dansyl side arm. The fluorescent sensor has been studied by potentiometric, UV-Vis, and emission studies in MeOH : water 3 : 2 mixture (0.07 M NaNO3), determining, in particular, the protonation constants of the free ligand and metal ion complexation equilibria. Interestingly, the obtained results revealed that the new receptor is fluorescent at neutral pH with a typical emission band of the dansyl group. Metal addition induced a partial quenching of the dansyl emission band; this behavior is more pronounced with Cu(II) that reduces the receptor’s emission by 60%. With all the studied cations, quenching follows the formation of a dimetallic complex. Similar studies on the model compound L2 confirmed that fluorescence quenching is mainly driven by a static mechanism, attributable to the formation of the inclusion dicopper complex [L1Cu2]4+. In order to test the stability of copper complexes under physiological conditions, spectrofluorimetric titrations with Cu(II) were performed in water buffered at pH = 8 (HEPES 0.07 M) and the values of binding constants, K11 and K12, were determined.
The monometallic nickel(II) complexes [Ni(H 2 nsh)(A) 2 ]·nH 2 O (where A = water (H 2 O), n=0 (1); pyridine (py), n=2 (2); 2-picoline(2-pic), n=0 (3); 3-picoline(3-pic), n=2 (4); and 4-picoline(4-pic), n=0 (5)) and homobimetallic nickel(II) complexes [Ni 2 (nsh)(A) 4 ]·nH 2 O (where A = water (H 2 O), n=1 (6); pyridine (py), n=4 (7); 2-picoline(2-pic), n=4 (8); 3-picoline(3-pic), n=4 (9); and 4-picoline(4-pic), n=4 (10), resp.) have been synthesized in methanol from bis(2-hydroxy-1-naphthaldehyde)succinoyldihydrazone (H 4 nsh). The complexes have been characterized by elemental analyses, molar conductance, magnetic moment, and electronic and IR and TGA/DTA spectroscopic studies. The monometallic complexes (1) to (5) are found to have octahedral stereochemistry while complexes (6) to (10) are found to have distorted octahedral stereochemistry in which one of the Ni(II) centres is present in N 2 O 2 coordination sphere and another Ni(II) centre is bonded to it through phenolate oxygen atoms via oxo-bridging.
A pentacoordinated mononuclear copper(II) complex, namely, bis(2,2′-bipyridine)sulphatecopper(II) urea trisolvate dihydrate, has been synthesised and characterised by molar conductance and UV-Vis and FTIR spectra. The structure of the complex was unambiguously confirmed by single crystal XRD. The complex crystallizes in monoclinic system, space group C2/c, with the values a = 20.155(4), b = 20.858(4), and c = 14.425(3) Å; α = 90.00°, β = 96.51°, and γ = 90.00°; V = 6025(2) Å3 and Z = 8. The Cu(II) ion is coordinated to four nitrogen atoms of two bidentate 2,2′-bipyridine ligands (bipy) and by one oxygen atom of the sulphate group and displays distorted trigonal bipyramidal geometry. The crystal packing is stabilized by inter- and intramolecular hydrogen bonding. The Cu(II) complex was screened for antimicrobial activity against Staphylococcus aureus, Escherichia coli, Klebsiella pneumonia, Aspergillus niger, Aspergillus flavus, and Candida albicans. Larvicidal activity of the synthesized copper(II) complex was carried out against larvae of Culex quinquefasciatus and Anopheles subpictus.
A novel one-dimensional coordination polymer bis(2-aminopyridine)-μ-bis(dicyanamido) cobaltate(II) has been synthesized and characterized by elemental analyses and infrared and ultraviolet visible spectroscopies and the structure has been determined by single crystal X-ray diffraction. Co(II) ion in the complex is coordinated to two axial 2-aminopyridine ligands through the pyridine N-atom and four equatorial dicyanamide ligands to give a CoN6 slightly distorted octahedral coordination environment around the metal ion. The amino N-atom forms intrachain hydrogen bonds. Antimicrobial screening of the complex against eight pathogenic microorganisms (four bacteria and four fungi) isolated from humans, indicates that the complex is moderately active.
The present paper deals with the synthesis and characterization of metal complex of tridentate Schiff base ligand derived from the inserted condensation of 2-aminobenzimidazole (1H-benzimidazol-2-amine) with salicylaldehyde (2-hydroxybenzaldehyde) in a 1 : 1 molar ratio. Using this tridentate ligand, complex of Zn(II) with general formula ML has been synthesized. The synthesized complex was characterized by several techniques using molar conductance, elemental analysis, FT-IR, and mass and 1HNMR spectroscopy. The elemental analysis data suggest the stoichiometry to be 1 : 1 [M : L]. The complex is nonelectrolytic in nature as suggested by molar conductance measurements. Infrared spectral data indicate the coordination between the ligand and the central metal ion through deprotonated phenolic oxygen, imidazole nitrogen of benzimidazole ring, and azomethine nitrogen atom. Spectral studies suggest tetrahedral geometry for the complex. The pure compound, synthesized ligand, and metal complex were screened for their antimicrobial activity.
Layered metal hydroxynitrates and mixed metal hydroxynitrates (copper/cobalt hydroxynitrates and zinc/cobalt hydroxynitrates at different mole ratios) were synthesized by hydrolysis of urea and metal nitrates at 140°C. Layered metal hydroxyl nitrates derive their structure from brucite mineral and generally crystallize in hexagonal and monoclinic phases. Isothermal decomposition studies of Cu2(OH)3(NO3), Co2(OH)3(NO3), Cu1.5Co0.5(OH)3(NO3), Cu1.34Co0.66(OH)3(NO3), Zn5(OH)8(NO3)2(H2O)2, Zn3.75Co1.25(OH)8(NO3)2(H2O)2, and Zn3.35Co1.65(OH)8(NO3)2(H2O)2samples were carried out at different intervals of temperature and the structural transformations during the process were monitored using powder X-ray diffractograms. Biphasic mixture of metal hydroxynitrate/metal oxide is observed in case of cobalt/zinc based layered hydroxynitrates, while copper hydroxynitrate or copper/cobalt metal hydroxynitrate decomposes in a single step. The decomposition temperatures of layered metal hydroxynitrates and mixed layered metal hydroxides depend on the method of preparation, their composition and the nature of metal ion, and their coordination.
Mixed ligand complexes of Fe(III) with aromatic thiohydrazides of general composition [Fe(acac)(L) 2 ] have been synthesized and characterized (acac-acetylacetonate, L = bidentate uninegative aromatic thiohydrazide ligand, for example, thiobenzhydrazide, 2-hydroxythiobenzhydrazide, furan-2-thiohydrazide, and thiophen-2-thiohydrazide). The magnetic susceptibility data and the EPR spectra of these complexes suggested the formation of rhombically distorted low spin iron center (d 5 ) in octahedral environment, which was also supported by the UV-vis spectral data of the complexes. Biological studies of these complexes also indicated that the iron-thiohydrazido complexes have superior antibacterial properties compared to the corresponding ligands.
Seven novel 4-vinylbenzyl substituted N-heterocyclic carbene (NHC) silver complexes were synthesized from different benzimidazolium salts and silver (I) oxide in dichloromethane at room temperature. These new 4-vinylbenzyl substituted NHC silver complexes were characterized by spectroscopic (NMR, IR) and elemental analysis techniques. Using the agar dilution procedure, the antimicrobial activities of these synthesized new compounds were investigated against Gram (+)/(−) bacterial and fungal strains. These NHC silver complexes showed effective activities against Escherichia coli, Pseudomonas aeruginosa (Gram-negative bacterial strains), Enterococcus faecalis, Staphylococcus aureus (Gram-positive bacterial strains), and Candida tropicalis and Candida albicans (fungal strains).
Five new mononuclear copper(II) complexes, namely, [Cu(L)(ImH)]·ClO 4 1 ; [Cu(L)(Me-ImH)]·ClO 4 2 ; [Cu(L)(Et-ImH)]·ClO 4 3 ; [Cu(L)(2-benz-ImH)]·ClO 4 4 ; [Cu(L)(benz-ImH)]·ClO 4 5 , where HL = 2-{[( Z )-phenyl (pyridine-2-yl) methylidene] amino} benzenethiol; ImH = Imidazole; Me-ImH = Methy-limidazole; Et-ImH = Ethyl-imidazole; 2-benz-ImH = 2-methyl-benzimidazole; benz-ImH = benz-imidazole, have been synthesized and characterized by various physicochemical and spectroscopic techniques. Magnetic moments, electronic spectra, and EPR spectra of the complexes suggested a square planar geometry around Cu(II) ion. The synthesized HL ligand behaves as monobasic tridentate Schiff base bound with the metal ion in a tridentate manner, with N 2 S donor sites of the pyridine-N, azomethine-N, and benzenethiol-S atoms. The redox behaviour of the copper complexes has been studied by cyclic voltammetry. Superoxide dismutase activity of these complexes has been revealed to catalyse the dismutation of superoxide (O2-) and IC 50 values were evaluated and discussed.
To aid in knowledge of macrocyclic complexes and biomedical scientists, we are presenting here a review article with compilation of work done so far along in relation to macrocyclic ligands and their metal complexes. The metal ion chemistry of macrocyclic ligands has now become a major subdivision of coordination chemistry. This overview focuses on developments in design, synthesis, and self-assembly of metal-based architectures and ligands related to macrocyclic chemistry.
The coordination complexes of bivalent metal ions with N-[(1E)-1-(1H-Benzimidazol-2-yl)ethylidene]morpholine-4-carbothiohydrazide (H2bmctz, H2L-1) and N-[(1E)-1-(1H-Benzimidazol-2-yl)(phenyl)methylidene] morpholine-4-carbothiohydrazide (H2bpmctz, H2L-2) were prepared and their neutral, monoanionic, and dianionic forms of ligands of compositions [M(H2L)X2] (M=CoII,NiII,CuII,ZnII,CdII, orPdII, X=Cl−or Br−, and H2L=H2L-1 or H2L-2), [M(HL)2]nH2O where (M=CoII,CuII,MnII,NiII,ZnIIorCdII, H2L=H2L-1 or H2L-2, andn= 0 or 2), and [MLB]nB (M=CuII,NiII,ZnII,CdII, orPdII, B=H2O, Py, orY-pic,n= 0 andn= 1 if B=H2O for Ni(II) and H2L=H2L-1 or H2L-2) have been characterised by magnetic susceptibility measurements, electrical conductance values, and spectral properties. The magnetic moment value of [M(HL2)] (M=MnII,NiII,FeIIorCuII) type complexes is consistent with high spin octahedral structure while those of [M(H2L)X2] (M=CoII,NiII,CuII,ZnII, orCdII, X=Cl−or Br−) possess five coordinated trigonal bipyramidal geometry. The adduct complexes [MLB]·nB (M=NiII, orCuII, B=H2O, Py, orY-pic) are four coordinated planar and those ofZnIIandCdIIcomplexes [MLB], (H2L=H2L-1 or H2L-2, B=H2O, Py orY-pic) are tetrahedral. These ligands have been suggested to coordinate as tridentate (N N S) donor molecule in complexes of type [M(H2L)X2], [M(HL)2], and [MLB]. The antifungal activity of ligands and some of their metal complexes were studied and it was observed that metal complexes show higher activity than free ligand.
Two new series of copper(II) and nickel(II) complexes with two new Schiff base ligands 2-((2,4-dimethylphenylimino)methyl)-6-methoxy-4-nitrophenol and 2-((3,4-difluorophenylimino)methyl)-6-methoxy-4-nitrophenol have been prepared. The Schiff base ligands were synthesized by the condensation of 2-hydroxy-3-methoxy-5-nitrobenzaldehyde with 2,4-dimethylaniline or 3,4-difluoroaniline. The ligands and their metal complexes have been characterized by IR, 1H NMR, mass and electronic spectra and TG analysis. The Schiff base ligands and their metal complexes were tested for antimicrobial activity against Gram positive bacteria Staphylococcus aureus, and Streptococcus pyogenes and Gram negative bacteria Escherichia coli, and Pseudomonas aeruginosa and fungus Candida albicans, Aspergillus niger, and Aspergillus clavatus using Broth Dilution Method.
Abstract - The kinetics of the oxidation of naphthol green B (NGB3-) by Cr2O7 2- has been studied in aqueous hydrochloric acid medium at an ionic strength, I = 0.50 mol dm-3 (NaCl), H+ =1.0 10-4 mol dm-3 (HCl) and T = 25 1C. The redox reaction displayed a stoichiometry of 1:1 and obeys the rate law: -dNGB3-/dt = k2NGB3-]Cr2O7 2- . The second order rate constant increases with increase in acid concentration and in the ionic strength of reaction medium. The rates of reaction displayed a positive salt effect. Addition of acrylonitrile to a partially reacted mixture in the presence of excess methanol did not lead to gel formation. Added cations and anions inhibited the naphthol green B - Cr2O7 2- reaction. Results of the Michaelis – Menten plot gave no evidence of intermediate complex formation during the course of the reaction. Based on the results obtained, the reaction is believed to proceed through the outersphere mechanistic pathway.Keywords: Intermediate; Redox; Pseudo-octahedral; Michaelis – Menton; Outersphere
Potentiometric studies in aqueous medium and spectrophotometric study in non-aqueous medium were used to understand the behavior of hexamethylenetetramine (HMTA) complexes. The protometric studies of HMTA enabled us to confirm that only one basic site of this ligand is protonated in acidic medium and this ligand is decomposed in acidic medium. In aqueous medium, only hexa-aqua complexes in which HMTA is present in the second coordination sphere forming H-bonds with hydrogen atoms of coordinated and uncoordinated water molecules are obtained. In non-aqueous solvents, HMTA coordinates to metal ions displaying diversity in the structures of the resulting complexes in which HMTA can either be monodentate, bridged bidentate, tridentate, or tetradentate.
Coordination complexes with metal ions Cu(II), Ni(II), Co(II), Fe(III), Mn(II), Cr(III), and VO(II) with six ligands formed by condensation products using azides and aldehydes or ketones are characterized. Both the ligands and the complexes synthesized are characterized by C, H, N, Cl and metal analyses, IR, UV-Vis, TGA, and magnetic susceptibility for tentative structure proposal. Several of them are screened for their toxicity (i.e., physiological activity) against fungal species Rhizoctonia solani and Acrocylindrium oryzae and a bacterium, Xanthomonas oryzae on rice pathogens. The study shows that the observed physiological activity is enhanced for the metal complexes as compared to the simple metal salts or ligands, except in the case of L3 or HAEP ligand, where the free –OH and –NH 2 groups on the ligand seemed to have inhibited the activity. It is also observed that the order of activity has a dependence on the increased atomic weight of the metal ion in use. In some cases, especially the VO(II) complexes, they are found to be better than the standards in use, both for the fungicides and for the bactericide.
The present paper deals with the synthesis and characterization of metal complexes of Schiff base derived from xipamide, a diuretic drug. The bidentate ligand is derived from the inserted condensation of 5-aminosulfonyl-4-chloro-N-2,6-dimethyl phenyl-2-hydroxybenzamide (Xipamide) with salicylaldehyde in a 1 : 1 molar ratio. Using this bidentate ligand, complexes of Hg(II), Zn(II), and VO(IV) with general formula ML 2 have been synthesized. The synthesized complexes were characterized by several techniques using molar conductance, elemental analysis, magnetic susceptibility, FT-IR spectroscopy, electronic spectra, mass spectra, and particle size analysis. The elemental analysis data suggest the stoichiometry to be 1 : 2 [M : L]. All the complexes are nonelectrolytic in nature as suggested by molar conductance measurements. Infrared spectral data indicate the coordination between the ligand and the central metal ion through deprotonated phenolic oxygen and azomethine nitrogen atoms. Spectral studies suggest tetrahedral geometry for Hg(II), Zn(II) complexes, and square pyramidal geometry for VO(IV) complex. The pure drug, synthesized ligand, and metal complexes were screened for their antifungal activities against Aspergillus niger and Aspergillus flavus . The ligand and its Hg(II) and VO(IV) complexes were screened for their diuretic activity too.
The main focus of this work had been to grow good quality crystals from amino acids and amino acid-based materials for nonlinear optics (NLO) applications. For the first time, a series of amino acid complexes doped with transition metal ions were grown in our laboratory from aqueous solutions by slow evaporation technique. Ni(II) ion doped Manganese L-Histidine hydrochloride monohydrate (Ni(II)-MnLHICl) crystals were grown on the same lines and were characterized by powder X-ray diffraction (XRD), optical absorption, electron paramagnetic resonance, and infrared absorption studies. From Powder XRD, the unit cell lattice parameters were calculated as a=1.5301 nm, b=0.8928 nm and c=0.6851 nm. From electron paramagnetic resonance (EPR) spectra, isotropic “ g ” factor and spin hamiltonian parameter A all were calculated as 2.0439 and 20×10−4, respectively. From optical absorption studies, crystal field splitting value (Dq) and the interelectron repulsion parameters B and C were calculated for Ni 2+ and Mn 2+ as Dq=850 cm −1 , B=725 cm −1 , C=2640 cm −1 and Dq=915 cm −1 , B=810 cm −1 , C=2780 cm −1 , respectively. The presence of various functional groups and the modes of vibrations were confirmed by FTIR studies.
