Synthesis,characterization and antibacterial activity of indium(III) complexes with adamantane-ring containing Schiff bases

Indium(III) chloride tetrahydrate and Schiff-base ligands derived from adamantaneamine and 3-/4-methoxysalicylaldehyde gave two complexes, C₂₂H₃₂Cl₃InN₂O₃ (1) and C₃₆H₄₄C_l3InN₂O₄ (2), respectively. The complexes were characterized by IR, ¹H NMR, elemental analysis, molar conductance, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, P2₁/n space group with the asymmetric unit consisting of one indium(III), one N-(3-methoxysalicylidene)-aminoadamantane (L¹), three chlorides and one N,N-dimethylformamide molecule. The indium is six-coordinate with reversed triangular-prism geometry via three oxygens and three chlorides. Complex 2 crystallizes in the triclinic system, P 1 space group; the asymmetric unit consists of one indium(III), two N-(4methoxysalicylidene)-aminoadamantane (L²), and three chlorides. The indium is five-coordinate with distorted trigonal-bipyramidal geometry via two oxygens and three chlorides. Antibacterial activities of the complexes have been investigated against Escherichia coli and Staphylococcus aureus.     

Tetradentate asymmetric Schiff bases and their Ni(II) and Fe(III) complexes

Three asymmetric Schiff-base tetradentate diimines H₂L¹, H₂L², and H₂L³ [(2-OH)C₆H₄N=CHC₆H₄2-N=CHC₆H₃(2-OH)(5-X), X?=?H, CH₃, Cl respectively] have been synthesized by a two step process. The reaction of 2-hydroxy aniline with 2-nitro-benzaldehyde in EtOH gave the starting Schiff base, 2-hydroxy-N-(2-nitrobenzylidene)aniline (SB-NO₂), which was reduced into the amino derivative (SB-NH₂) in solution. Reacting SB-NH₂ with 2-hydroxybenzaldehyde, 2-hydroxy-5-methylbenzaldehyde and 2-hydroxy-5-chlorobenzaldehyde gave the three new ligands H₂L¹, H₂L², and H₂L³ respectively. Their dimeric, binuclear metal complexes with Ni(II) and Fe(III) have also been synthesized. The ligands and their complexes were characterized by elemental analyses, LC–MS, IR, electronic, ¹H and ¹³C-NMR spectra, TGA, conductivity and magnetic measurements. All of the spectroscopic, analytical and other data indicate octahedral geometry M₂L₂(H₂O)X₂ (M: Ni,Co;X: Cl or H₂O), except for NiL² which is monomeric. Antimicrobial activities of the ligands and the complexes were evaluated against five bacteria. While the ligands and the Ni complexes are inactive towards Pseudomonas aeruginosa and Staphylococcus aureus, Fe complexes are active; only Fe complexes are inactive against Escherichia coli. All of the compounds have antimicrobial activities against Bacillus subtilis, and Yersinia enterecolitica.     

Synthesis,structural characterization and biological studies of neodymium(III) and samarium(III) complexes with mercaptotriazole Schiff bases

A series of neodymium(III) and samarium(III) complexes of type [Ln(L)Cl(H₂O)₃] have been synthesized with Schiff bases (LH₂) derived from 3‐(phenyl/substituted phenyl)‐4‐amino‐5‐mercapto‐1,2,4‐triazoles and isatin. The structures of the complexes were established using elemental analysis, molar conductivities, magnetic moments, infrared, NMR (¹H, ¹³C) and UV–visible spectra, X‐ray diffraction and mass spectrometry. The thermal behaviour of these compounds under non‐isothermal conditions was investigated using thermogravimetry and differential thermogravimetry. The intermediates obtained at the end of various thermal decomposition steps were identified from elemental analysis and infrared spectral studies. All the ligands and their complexes were also screened for their antibacterial activity against Staphylococcus aureus and Bacillus subtilis and antifungal activity against Aspergillus niger, Aspergillus flavus and Colletotrichum capsici. The screening results were correlated with the structural features of the compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

New complexes of lanthanide Ln(III), (Ln = La, Sm, Gd, Er) with Schiff bases derived from 2-furaldehyde and phenylenediamines

Some new Schiff bases derivates from 2-furaldehyde and phenylenediamines (L^1-3) and their complexes with lanthanum (La), samarium (Sm), gadolinium (Gd) and erbium (Er) have been synthesized. These complexes with general formula [Ln(L^1-3)₂(NO₃)₂]NO₃·nH₂O (Ln = La, Sm, Gd, Er) were characterized by elemental analysis, UV-Vis, FT-IR and fluorescence spectroscopy, molar conductivity and thermal analysis. The metallic ions were found to be eight coordinated. The emission spectra of these complexes indicate the typical luminescence characteristics of the Sm(III), La(III), Er(III) and Gd(III) ions.     

Ortho-metallated ruthenium(III) complexes with some acid hydrazide based Schiff bases

Ortho-metallated ruthenium(III) complexes with Schiff bases (H₂L) derived from one mole equivalent each of benzaldehyde and acid hydrazides are described. Reactions of H₂L with [Ru(PPh₃)₃Cl₂] in presence of NEt₃ (1:1:2 mole ratio) under aerobic conditions in methanol provide the complexes having the general formula trans-[Ru(L)(PPh₃)₂Cl] in 55-60% yields. The complexes have been characterized with the help of elemental analysis, magnetic susceptibility, electrochemical and various spectroscopic (infrared, electronic and EPR) measurements. The +3 oxidation state of the metal centre in these complexes is confirmed by their one-electron paramagnetic nature. Molecular structures of two representative complexes have been determined by X-ray crystallography. In each complex, the metal ion is in a distorted octahedral CNOClP₂ coordination sphere. The dianionic C,N,O-donor ligand (L²⁻) together with the chloride form a CNOCl square-plane and the P-atoms of the two PPh₃ molecules occupy the two axial sites. The electronic spectra of the complexes in dichloromethane solutions display several absorptions due to ligand-to-metal charge transfer and ligand centred transitions. In dichloromethane solutions, the complexes display a ruthenium(III) → ruthenium(IV) oxidation in the potential range 0.35-0.98 V (vs. Ag/AgCl). All the complexes in frozen (110 K) dichloromethane-toluene (1:1) solutions display rhombic EPR spectra.     

Synthesis,spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

New metal based triazoles (1–12) have been synthesized by the interaction of novel Schiff base ligands (L¹–L³) with the Co(II), Ni(II), Cu(II) and Zn(II) metal ions. The Schiff base ligands and their all metal(II) complexes have been thoroughly characterized using various physical, analytical and spectroscopic techniques. In vitro bacterial and fungal inhibition studies were carried out to examine the antibacterial and antifungal profile of the Schiff bases in comparison to their metal(II) complexes against two Gram‐positive, four Gram‐negative and six fungal strains. The bioactivity data showed the metal(II) complexes to have more potent antibacterial and antifungal activity than their uncomplexed parent Schiff bases against one or more bacterial and fungal species. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermogravimetric and spectroscopic studies on La(III) and Ce(III) complexes with some thio-schiff bases

Solid complexes of five derivatives of thio-Schiff bases with La(III) and Ce(III) ions were prepared and characterized by elemental and thermogravimetric analyses. The suggested general formula of the solid complexes is [ML₂(H₂O)X]·2H₂O, whereM=trivalent lanthanide ion,L=Schiff base andX=Cl^? or ClO ₄ ^? . Information about the water of hydration, the coordinated water molecules, the coordination chemistry and the thermal stability of these complexes was obtained and is discussed. Additionally, a general scheme of thermal decomposition of the lanthanide-Schiff base complexes is proposed.     

Synthesis,characterization, and spectroscopic studies of tetradentate Schiff base chromium(III) complexes

Eight chromium(III) complexes of tetradentate Schiff bases have been prepared in situ by condensing of a substituted salicylaldehyde compound with ethylenediamine. These were characterized by elemental analysis, m.p., IR, molar conductivity, magnetic moment measurements, and electronic spectra. The free ligands were also characterized by ¹H and ¹³C NMR spectra. The ¹³C NMR spectra are discussed in terms of possible substituent effects. The IR and electronic spectra of the free ligand and the complexes are compared and discussed. The electrospray ionization (ESI) mass spectra of four free ligands and their complexes were measured. The deconvolution of the visible spectra of the complexes, C_2v symmetry, in DMSO yields three peaks at ca. 15 600–17 600, 18 400–20 400 and 20 000–23 100, and are assigned to the three d–d transitions, ⁴B_1g → ⁴E_g(⁴T_2g); ⁴B_1g → ⁴B_2g(⁴T_2g); ⁴B_1g → ⁴E_g(⁴T_1g), respectively. The complexes showed magnetic moment in the range of 3.5–4.2 BM which corresponds to three unpaired electrons.     

Synthesis,characterization and biological properties of novel ON donor bidentate Schiff bases and their copper(II) complexes

Four novel ON donor Schiff bases (E)-3-((4-phenoxyphenylimino)methyl)benzene-1,2-diol (HL₁),(E)-3-((4-(4-biphenyloxy)phenyliminomethyl)benzene-1,2-diol (HL₂), (E)-3-((4-naphthoxyphenylimino)methyl)benzene-1,2-diol (HL₃), (E)-3-((4-(2-naphthoxy)phenylimino)methyl)benzene-1,2-diol (HL₄) and their copper(II) complexes bis((E)-3-((4-phenoxyphenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L₁)₂) bis((E)-3-((4-(4-biphenyloxy)phenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L₂)₂), bis((E)-3-((4-naphthoxyphenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L₃)₂), bis((E)-3-((4-(2-naphthoxy)phenylimino)methyl)benzene-1,2-diol) copper(II) (Cu(L₄)₂) have been synthesized and characterized by spectroscopic (FTIR, NMR, UV–visible) and elemental analysis. The crystal structures of HL₁, HL₂, HL_3, and HL₄ have been determined, which reveal intramolecular N-H?O (HL₁, HL₂, HL_3, and HL₄) hydrogen bonds in the solid state. Keto-amine and enol-imine tautomerism is exhibited by the Schiff bases in solid and solution states. The Schiff bases and their copper(II) complexes have been screened for their biological activities. In antimicrobial assays (antibacterial and antifungal), HL₄ showed promising results against all strains through dual inhibition property while the rest of the compounds showed activity against selective strains. On the other hand, in cytotoxic, DPPH, and inhibition of hydroxyl (OH) free radical-induced DNA damage assays, the results were found significantly correlated with each other, i.e. the ligands HL₁ and HL₂ showed moderate activity while their complexes Cu(L₁)₂ and Cu(L₂)₂ exhibited prominent increase in activity. As the results of these assays are supporting each other, it represents the strong positive correlation and antioxidant nature of investigated compounds.     

Ruthenium(II) complexes containing bidentate Schiff bases and triphenylphosphine or triphenylarsine

Reactions of ruthenium(II) complexes [RuHX(CO)(EPh₃)₂(B)] (X = H or Cl; B = EPh₃, pyridine (py) or piperidine (pip); E = P or As) with bidentate Schiff base ligands derived by condensingo- hydroxyacetophenone with aniline,o- orp-methylaniline have been carried out. The products were characterized by analytical, IR, electronic and¹H-NMR spectral studies and are formulated as [Ru(X)(CO) (L)(EPh₃)(B)] (L = Schiff base anion; X = H or Cl; B = EPh₃, py or pip; E = P or As). An octahedral structure has been tentatively proposed for the new complexes. The new complexes were tested for their catalytic activities in the oxidation of benzyl alcohol to benzaldehyde.     

Synthesis,characterization and biological studies of oxovanadium(IV) complexes with triazole‐derived Schiff bases

A series of triazole‐derived Schiff bases (L¹–L⁵) and their oxovanadium(IV) complexes have been synthesized. The chemical structures of Schiff bases were characterized by their analytical (CHN analysis) and spectral (IR, ¹H and ¹³C NMR and mass spectrometry) data, and oxovanadium(IV) complexes were elucidated by their physical (magnetic susceptibility and conductivity), analytical (CHN analysis), conductance measurements and electronic spectral data. The molar conductivity data indicate the oxovanadium(IV) complexes to be non‐electrolyte. The Schiff bases act as bidentate and coordinate with the oxovanadium(IV)‐forming stoichiometry of a complex as [M (L‐H)₂] where M = VO and L = L¹–L⁵ in a square‐pyramidal geometry. The agar well diffusion method was used for in vitro antibacterial screening against E. coli, S. flexenari, P. aeruginosa, S. typhi, S. aureus and B. subtilis and for antifungal activity against T. longifucus, C. albican, A. flavus, M. canis, F. solani and C. glaberata. The biological activity data show the oxovanadium(IV) complexes to be more antibacterial and antifungal than the parent Schiff bases against one or more bacterial and fungal strains. Copyright © 2009 John Wiley & Sons, Ltd.     

New chelated complexes of bis-β-carboalkoxyethyltin(IV) dichloride with S-benzyldithiocarbazate Schiff bases

The Schiff bases [H₂SBSaD], [H₂SBVD] and [H₂SBND], derived by the condensation of S-benzyldithiocarbazate and salicylaldehyde, 2-hydroxy-3-methoxybenzaldehyde and 2-hydroxy-1-naphthaldehyde respectively, react with diestertin dichlorides, R₂SnCl₂ [R=? CH₂CH₂CO₂CH₃, ? CH₂CH₂CO₂C₂H₅ or ? CH₂CH₂CO₂C₄H₉] in 1:1 molar proportion to yield chlorine-substituted complexes of the type R₂Sn(Schiff base), the base being tridentate. The complexes are characterized on the basis of their elemental analyses, IR and ¹H NMR spectral studies. The ¹³C and ¹¹⁹Sn NMR and the tin-carbon coupling constant data reveal the structures of the complexes to be octahedral with trans ester grouping, and bidentate ester linkages. The pentacoordinated complex (CH₃)₂Sn(SBSaD) was prepared by the reaction of dimethyltin oxide with H₂SBSaD in equimolar proportions.     

New immobilized Schiff bases

In this study, three new immobilized Schiff bases and their Co(II), Cu(II) and Ni(II) metal complexes have been prepared. The ligands silica-Si[N-(3-propyl)2,4-dihydroxybenzaldimine] (1) H₂L, silica-Si[N-(3-propyl)4-methylsalicylaldimine-3-methoxy] (2) HL and silica-Si[N-(3-propyl)2-pyridinecarboxyaldimine] (3) L have bidentate characters. Therefore, the complexes are the mononuclear. Ligands and metal complexes were characterized by FTIR, AAS and thermoanalytical techniques. On the basis of analytical data and IR studies, a 1:1 metal to ligand stoichiometry has been suggested. TG and DTA results showed that these ligands and complexes had good thermal stability. The heat capacities of ligands were reported in the temperature range 273–363 K as no thermal anomaly was found in this temperature range.     

Zinc(II) complexes with Schiff bases derived from ethylenediamine and salicylaldehyde: the synthesis and photoluminescent properties

The effect of the nature of organic ligands and complex formation on the photoluminescent characteristics (relative quantum yield, excited-state lifetime) and thermal stability of tetradentate Schiff bases (H₂L), derivatives of salicylaldehyde (H₂(SAL)¹, H₂(SAL)²), o-vanillin (H₂(MO)¹, H₂(MO)²) with ethylenediamine and o-phenylenediamine, and their zinc(II) complexes was studied. Zinc(II) complexes were synthesized by the reaction of H₂L with Zn(AcO)₂·2H₂O in MeOH at room temperature or under reflux. In the case of H₂L = H₂(SAL)², H₂(MO)¹, H₂(MO)², complexes of the composition ZnL·H₂O were isolated irrespective of the temperature. For H₂L = H₂(SAL)¹, the reaction results in Zn(SAL)¹·H₂O at room temperature and in anhydrous dimeric complex [Zn(SAL)¹]₂ under reflux. Density functional calculations of H₂L and ZnL confirmed that (1) luminescence of these compounds is due to the π-π* transition between orbitals of the organic ligand and (2) enhancement of conjugation of the chain and introduction of electron-donating substituents lead to a decrease of the energy gap and, there-fore, to a bathochromic shift of the emission maximum. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1846–1855, September, 2008.     

Synthesis,characterization, and crystal structure of three cobalt(II) complexes with Schiff bases derived from rimantadine

By condensation of rimantadine and substituted salicylaldehyde, three new Schiff bases, HL¹, HL² and HL³, were synthesized. Then, a mixture of one of the new ligands and cobalt(II) chloride hexahydrate in ethanol led to 1, 2, and 3, respectively. These complexes were characterized by melting point, elemental analysis, infrared spectra, molar conductance, thermal analysis, and single-crystal X-ray diffraction analysis. X-ray diffraction analysis reveals that 1 crystallizes in the orthorhombic system, Pbcn space group; each asymmetric unit consists of one cobalt(II) ion, two deprotonated ligands, and one lattice water. The central cobalt is four coordinate via two nitrogens and two oxygens from the corresponding Schiff base ligand, forming a distorted tetrahedral geometry. Complexes 2 and 3 crystallize in the monoclinic system, P2₁/c space group; each asymmetric unit consists of one cobalt(II), two corresponding deprotonated ligands, one lattice water, and one methanol. The central cobalt is also four-coordinate via two nitrogens and two oxygens from the corresponding Schiff base ligand, forming a distorted tetrahedral geometry.     

Synthesis and catalytic activity of novel heteronuclear Ln (III) -Cu(II) complexes with noncyclic polyether-amino acid Schiff base

A series of novel heteronuclear Ln(III)-CU(II) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is (LnCu₂(H₂TALY) (NO₃)₅] (NO₃)₂·nH₂O (Ln= La, Nd, Sm, Gd,n = 4; Ln = Yb, Y,n = 3), where H₂TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(II) complexes and Ln(III)-Cu(II) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra. TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst. which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bases can be used as a good catalyst, which has been confirmed and discussed here. They may be a new kind of catalyst system with the above speciality. Project supported by the National Natural Science Foundation of China (Grant No. 29671026) and Natural Science Foundation of Zhejiang Province (Grant No. 296062) and the Laboratory of MRAMP (Grant No. 971502).     

Synthesis and characterization of pentagonal bipyramidal organotin(IV) complexes of 2,6-diacetylpyridine Schiff bases of S-alkyl- and aryldithiocarbazates

New organotin(IV) complexes with empirical formula Sn(SNNNS)R₂, where SNNNS is the dianionic form of 2,6-diacetylpyridine Schiff bases of S-methyldithiocarbazate (H₂dapsme) or S-benzyldithiocarbazate (H₂dapsbz) and R = Ph or Me, have been prepared and characterized by IR, UV-Vis, NMR and Mössbauer spectroscopic techniques and conductance measurements. The molecular structures of the Sn(dapsme)R₂ (R = Ph and Me) have been determined by single crystal X-ray diffraction techniques. Both complexes have a distorted pentagonal-bipyramidal geometry in which the tin is coordinated by a dinegatively charged pentadentate chelating agent via pyridine nitrogen, two azomethine nitrogens, and two thiolate sulfurs. The five donors (N₃S₂) provided by the Schiff base occupy the equatorial plane close to a pentagonal planar array while the carbanion ligands occupy axial sites.     

Synthesis and characterization of reactive liquid crystalline Schiff bases,Rh(I) complexes,and their derived polymers

Two series of salicylaldimines have been synthesized that consist of model compounds with terminal methylenic chains and reactive compounds in which the terminal chains have been modified with acrylate groups. The dicarbonylrhodium(I) complexes of these systems were prepared by reacting the ligands with the dimer [RhCl(cod)]₂ and CO. Characterization of the metal‐containing acrylates by ¹H NMR spectroscopy revealed that the Rh(I) can coordinate to the terminal double bond to produce pentacoordinated complexes. Furthermore, investigation of the mesogenic properties of the complexes revealed that the bulkiness of the metallic center requires the presence of at least a three‐ring aromatic core to avoid the suppression of liquid crystallinity. The study was extended to include the side‐chain polymers obtained from the acrylate‐functionalized Schiff bases. Chelation of the preformed polyacrylate with low percentages of Rh(I) emerged as the best strategy to prepare Rh(I)‐containing polyacrylates. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4466–4477, 2000     

Synthesis and characterization of Ni(II) complexes of O,N-donor Schiff bases derived from acyl pyrazolone analogues

Two bidentate Schiff bases, 5-methyl-2-p-tolyl-4-(1-p-tolylimino-propyl)-2H-pyrazol-3-ol (L1) and 2-(3-chloro-phenyl)-5-methyl-4-(1-p-tolylimino-propyl)-2H-pyrazol-3-ol (L2), were synthesized by condensation of 4-acyl pyrazolones with p-toluidine in ethanol. These ligands have been characterized by elemental analysis, infrared (IR), ¹H NMR, and mass spectra. A single crystal molecular structure of ligand L2 was also solved. Nickel(II) complexes of these ligands with general formula [ML₂?·?2H₂O] have been prepared by the interaction of aqueous solution of Ni-acetate with ethanolic solution of the appropriate ligand. The complexes were separated, analyzed, and their structures were elucidated on the basis of elemental analysis, Ni(II) determination, IR, UV-Vis, conductance, mass, and TGA-DTA data. Octahedral structure was proposed for the synthesized complexes.     

Synthesis,characterization, and in vitro antioxidant and anticancer studies of ruthenium(III) complexes of symmetric and asymmetric tetradentate Schiff bases

Ruthenium(III) complexes of three tetradentate Schiff bases with N₂O₂ donors formulated as [RuCl(LL¹)(H₂O)], [RuCl(LL²)(H₂O)] and [RuCl(LL³)(H₂O)] were synthesized and characterized by elemental analyses, molar conductance, FTIR, and electronic spectral measurements. The FTIR data showed that the tetradentate Schiff base ligands coordinate to Ru ions through the azomethine nitrogen and enolic oxygen. The antioxidant activities of the complexes were investigated through scavenging activity on 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radicals. The DPPH activity for [RuCl(LL²)(H₂O)] with IC₅₀ = 0.031 mg mL^?1 was higher than the values obtained for the other Ru(III) compounds. The study revealed that the synthesized Ru(III) complexes of the tetradentate Schiff base exhibited strong scavenging activities against DPPH and moderate against ABTS radicals. In addition, the antiproliferative studies of the complexes were also tested against human renal cancer cells (TK10), human melanoma cancer cells (UACC62), and human breast cancer cells (MCF7) using the SRB assay. The results indicated that the Ru(III) complexes showed low anticancer activities against the tested human cancer cell lines.