Organotin(IV) complexes of dibasic tridentate Schiff bases containing ONO donor atoms

Organotin(IV) Schiff base complexes of the type (L)SnR₂ [where R?CH₃, C₆H₅ or CH₂CH₂CO₂ CH₃], (LH)Sn(C₆H₅)₃ and (L)SnCl(CH₂CH₂CO₂ CH₃) [where LH₂?2-N-salicylideneimino-2-methyl-1-propanol, derived from the condensation of salicylaldehyde and 2-amino-2-methyl-1-propanol] have been prepared and characterized on the basis of their elemental analyses, IR, ¹H, ¹³C and ¹¹⁹Sn NMR studies. In these mononuclear complexes the Schiff base acts either as a dianionic tridentate or as a monobasic bidentate moiety by coordinating through an alkoxy group, an azomethine nitrogen and a phenoxide ion to tin. Sulphur dioxide inserts in the tin–methyl/–phenyl bond in the above Schiff base complexes to give tin–O–sulphinates of formulae (L)RSn(SO₂R) and (LH)(C₆H₅)₂Sn(SO₂C₆H₅).     

Synthesis,characterization and antimicrobial activity of a bidentate NS Schiff base of S-benzyl dithiocarbazate and its divalent complexes

The reaction of S-benzyl dithiocarbazate (SBDTC) with 2,4,5-trimethoxybenzaldehyde afforded a bidentate NS Schiff base 1 (benzyl-3-N-(2,4,5-trimethoxyphenylmethylenehydrazine carbodithioate), which on further reaction with M(II) (where M(II) = nickel(II), zinc(II), palladium(II) and copper(II)) in ethanol under reflux yielded bis-chelated inner complexes [ML₂] 2–5 with deprotonated L. The ligand and its complexes were characterized by physicochemical techniques, viz., molar conductance, magnetic susceptibility measurement, IR, NMR, UV–Vis and mass spectroscopic techniques. The crystal structures of 1 and 5 were also determined by single-crystal X-ray crystallography. The crystal structure analysis showed that the ligand exists in its thione tautomeric form. In the complexes, each of the two deprotonated ligands chelated the metal ions through the β-nitrogen and the thione sulfur forming five-membered rings. The copper(II) complex (5) exhibited a square-planar geometry, where the two N₂S₂ chromophores are arranged trans. All the compounds showed strong antibacterial activity against S.-β-hemolyticus, Klebsiella pneumoni, and Escherichia coli. The compounds also showed strong antifungal activity against Aspergillus fumigatus, Aspergillus niger, Aspergillus flavus, and Candida albicans with the exception of the palladium(II) complex (4) which showed no activity, while all the compounds showed no activity against Fusarium vasinfectum.     

Synthesis and characterization of polystyrene-anchored monobasic bidentate Schiff base and its complexes with bi-, tri-, tetra- and hexavalent metal ions

A new monobasic bidentate ON donor Schiff base PS–LH₂ (where PS–LH₂ = polystyrene-anchored Schiff base obtained by condensation of chloromethylated polystyrene (containing 1.17 mmol of chlorine per gram of resin cross-linked with 2% divinylbenzene), 2-hydroxy-1-naphaldehyde and 4-aminosalicylic acid has been synthesized. PS–LH₂ reacts with metal complexes to form polystyrene-anchored complexes: PS–LHM(CH₃Coo) · DMF (where M = Cu, Zn, Cd, UO₂), PS–LHZr(OH)₂(CH₃Coo) · 2DMF, PS–LHFeCl₂ · 2DMF, PS–LHM′(CH₃Coo) · 3DMF (where M′ = Mn and Ni) and PS–LHMoo₂(acac), where acacH = acetylacetone. The polystyrene-anchored complexes have been characterized by elemental analysis, IR, ESR and magnetic susceptibility measurements. The per cent reaction conversion of PS–LH₂ to polystyrene supported coordination compounds lies between 30–95. Shifts of the azomethine ν(C=N) and phenolic ν(C–O) stretches are indicative of ON donor behaviour of the polystyrene-anchored ligands. The complexes, PS–LHCu(CH₃Coo) · DMF, PS–LHFecl₂ · 2DMF, PS–LHMn(CH₃Coo) · 3DMF and PS–LHNi(CH₃Coo) · 3DMF are paramagnetic, while PS–LHZn(CH₃Coo) · DMF, PS–LHCd(CH₃COO) · DMF, PS–LHUo₂(CH₃Coo) · DMF, PS–LHZr(OH)₂(CH₃COO) · 2DMF and PS–LHMoO₂(acac) are diamagnetic. The copper(II) complex exhibits a square planar structure, zinc(II) and cadmium(II) complexes have tetrahedral structures, nickel(II), manganese(II), iron(III), dioxomolybdenum(VI) and dioxouranium(VI) complexes have octahedral structure and zirconium(IV) complex is pentagonal bipyramidal.     

Transition metal complexes of bidentate p-tert-butylcalix[4]arene S-alkyldithiocarbazate Schiff bases

The calix[4]arene-based podand, which incorporates two Schiff-base functions derived from S-alkyldithiocarbazate in 1,3-alternate positions on the lower rim has been prepared and reacted with transition metal ions. X-ray single crystal diffraction of nickel and copper complexes shows that two iminothiolate domains are monoanionic bidentate planar chelators to coordinate one metal in distorted tetrahedral geometry.     

Spectroscopic characterization and electrochemical studies of ruthenium(II) carbonyl complexes containing bidentate Schiff bases and triphenylphosphine or a nitrogen heterocycle

Reactions of ruthenium(II) carbonyl complexes of the type [RuHCl(CO)(PPh₃)₂(B)] [B?=?PPh₃, pyridine (py), piperidine (pip) or morpholine (mor)] with bidentate Schiff base ligands derived from the condensation of 2-hydroxy-1-naphthaldehyde with aniline, o-, m- or p-toluidine in a 1?:?1 mol ratio in benzene resulted in the formation of complexes formulated as [RuCl(CO)(L)(PPh₃)(B)] [L?=?bidentate Schiff base anion, B?=?PPh₃, py, pip, mor]. The complexes were characterized by analyses, IR, electronic and ¹H NMR spectroscopy, and cyclic voltammetric studies. In all cases, the Schiff bases replace one molecule of phosphine and a hydride ion from the starting complexes, indicating that Ru–N bonds in the complexes containing heterocyclic nitrogenous bases are stronger than the Ru–P bond to PPh₃. Octahedral geometry is proposed for the complexes.     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

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.     

Some divalent metal(II) complexes of salicylaldehyde‐derived Schiff bases: Synthesis,spectroscopic characterization,antimicrobial and in vitro anticancer studies

Mononuclear transition metal(II) complexes of the type M(L)₂?2H₂O (where M = Co, Ni, Cu, Zn) have been synthesized from uninegative Schiff base ligands (HL₁–HL₄) designed by condensation of 4‐fluorobenzylamine with 2‐hydroxy‐1‐naphthaldehyde/3,5‐dichlorosalicylaldehyde/3,5‐dibromosalicylaldehyde/3‐bromo‐5‐chlorosalicylaldehyde. The compounds were successfully characterized using spectroscopic and physiochemical methods together with elemental analysis. Spectroscopic elucidation indicates a monobasic bidentate nature of ligands coordinated via deprotonated phenolic oxygen and azomethine nitrogen atom which suggests an octahedral geometry around the central metal ions. The complexes and ligands were screened for their in vitro antimicrobial activity against bacterial and fungal strains, the zinc(II) complexes being more active against the tested microbial strains. Further, the metal complexes were found to be more active than the uncomplexed ligands due to chelation process and, moreover, the complexes were more active against fungal strains than bacterial strains. Cytotoxic activities of all compounds were evaluated towards human alveolar adenocarcinoma epithelial cell line (A549), human breast adenocarcinoma cell line (MCF7), human prostate cancer cell line (DU145) and one normal human lung cell line (MRC‐5) using MTT colorimetric assay with doxorubicin as a standard. The zinc complexes were most active against the cancer cell lines and also found to be less toxic against MRC‐5 normal cell line than standard doxorubicin.     

Synthesis,spectroscopic characterization,biological screening and in vitro cytotoxic studies of 4‐methyl‐3‐thiosemicarbazone derived Schiff bases and their Co (II), Ni (II), Cu (II) and Zn (II) complexes

A series of twenty compounds inclusive of bidentate Schiff bases derived from condensation of 4‐methyl‐3‐thiosemicarbazide with substituted derivatives of napthaldehyde/benzaldehyde/salicylaldehyde and their mononuclear Co (II), Ni (II), Cu (II) and Zn (II) complexes in molar ratio (1:1) were synthesized and characterized. The coordination behavior, modes of bonding and overall geometry of the compounds was known from the elemental analysis, spectral techniques (IR, UV–Vis, ¹H NMR, ¹³C NMR, ESR and ESI‐mass), magnetic moment measurements, molar conductance, thermal and powder XRD studies. The studies revealed octahedral geometry for all the complexes where ligands coordinated in a neutral bidentate manner (NS) via nitrogen atom of azomethine group and sulphur atom of thione group with the metal centre. In vitro biological effects of the compounds were tested against four bacterial species and two fungal strains. The results indicated that the metal complexes showed a marked enhancement in biocidal activity in comparable with the parent Schiff bases. In vitro anticancer activity against the malignant tumor cell lines; human alveolar adenocarcinoma epithelial cell line (A549), human breast adenocarcinoma cell line (MCF7), human prostate cancer cell line (DU145) and human normal lung cell line (MRC‐5) using MTT assay, exposed compound 16 as a leading member with lowest IC₅₀ value of 10.6 ± 0.14 μM against (A549) cell line.     

源自天然席夫碱的过渡金属配合物在分光光度法测天然水中的Fe(Ⅲ)的应用

描述了一种新颖、简便的合成含五齿配位基的大环席夫碱配体的方法,制备和表征了该席夫碱的1∶1包合物。用化学和光谱学方法测定了标题配合物的组成,认为在所有配合物中配位金属原子取八面体结构。数据表明:配体起O2N4六齿结构而每个环绕金属原子在八面体环境中。配合物的红外和1H NMR光谱符合中心金属原子的配位结果。用分光光度法测定了配合物的稳定常数。用共轭余量法(CR method)计算了在热分解的不同阶段配合物活化的动力学和热力学参数。此外,用抑菌圈直径法筛选了配体及其金属配合物抑制细菌和真菌的能力。用回收率试验研究了天然螯合配体在不同天然水体中对Fe(Ⅲ)离子配合作用的影响。     

EPR character of gadolinium complexes with noncyclic polyether Schiff bases and its solvent effects

EPR characters of three new gadolinium complexes with noncydic polyether Schiff bases in powder or organic solvents, including various oxyethylene chain lengths and different substituting groups in ligands, are investigated respectively. Some regularities are summed up. The difference of EPR character in various solvents, particularly at different temperatures, has been examined. The 'single peak effect' due to THF solvent at low temperature is observed for the first time. This phenomenon is explicated.     

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.     

Nickel(II) complexes with Schiff bases derived from salicylaldehyde or pentanedione and 3-aminopropanethiol

Template reactions of salicylaldehyde or pentanedione with 3-aminopropanethiol (Hapt) in the presence of Ni(II) ions are described. When salicylaldehyde was used, a dinuclear Ni(II) complex [Ni(bit′)]₂ (2) (H₂bit′?=?2-(3′-mercaptopropyliminomethyl)phenol) was obtained instead of the reported trinuclear one [Ni(bit)]₃ (1) (H₂bit?=?2-(2′-mercaptoethyliminomethyl)phenol) containing 2-aminoethanethiol (Haet). Starting from pentanedione, the expected dinuclear complex [Ni(pit′)]₂ (H₂pit′?=?2-(3′-mercaptopropylimino)pentanol) was not obtained, nor was [Ni(pit)]₂ (3) (H₂pit?=?2-(2′-mercaptoethylimino)pentanol). The complex was found to be a trinuclear Ni(II) complex [Ni{Ni(apt)₂}₂]²⁺ (4), as confirmed by elemental analysis, electronic and NMR spectra. Complexes 1 and 3 were also synthesized and their ¹³C, ¹H–¹H and ¹³C–¹H?NMR spectra are discussed in detail. The X-ray crystal structure of 2 shows that two Ni(II) ions are connected by the thiolate donor atom from each ligand, resulting in a four-membered ring. Differences in reactivity and properties is due to the presence of an additional methylene group in the aminoalkane arm of the ligand.     

The structures and cyclic voltammetry of three copper(II) complexes derived from bulky ortho-hydroxy Schiff bases

Three copper(II) complexes derived from bulky ortho-hydroxy Schiff base ligands, (1)-(3), were synthesized and characterized by chemical analysis, UV-Vis, IR, μ_eff and mass spectrometry. The solid state structures of compounds (1)-(3) were determined. The solid state X-ray diffraction studies of these compounds show that the geometry is intermediate between square planar and tetrahedral. Moreover, EPR studies in DMF solution at 77 K suggest that the geometry of these complexes in solution is different from that observed in the solid state by X-ray crystallography. Furthermore, cyclic voltammetry studies performed for (1)-(3), indicate a dependence of the cathodic potentials upon conformational and electronic effects.     

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.     

Preparation,characterization and biological evaluation of copper(II) and zinc(II) complexes with Schiff bases derived from amoxicillin and cephalexin

Copper(II) and zinc(II) complexes of Schiff bases obtained by condensation of amoxicillin and cephalexin with salicylaldehyde/pyridoxal were prepared and characterized by microanalytical, thermogravimetric, magnetic and spectroscopic data. All the complexes were found to be six‐coordinate and containing two water molecules. The electron paramagnetic resonance spectral lines exhibited rhombic distortion from axial symmetry, with g_|| > g_? > g_e, in the copper(II) complexes. The geometry of the zinc(II) complexes appears to be octahedral. All the compounds under investigation showed antibacterial activity. The antibacterial activity showed the following trend: copper(II) complexes > zinc(II) complexes > Schiff base ligands > parent drugs. The copper(II) complexes with the Schiff bases derived from cephalexin showed substantially enhanced activity against Pseudomonas aeruginosa compared with the parent drug. All the copper complexes were also found to be active against kaolin paw oedema, whereas the parent drugs were inactive. Copyright © 2005 John Wiley & Sons, Ltd.     

In vitro antimicrobial and antioxidant evaluation of rare earth metal Schiff base complexes derived from threonine

Six novel Ln(III) Schiff base complexes were synthesized using rare earth metals with threonine and 5‐bromosalicylaldehyde, namely Pr(III), Sm(III), Gd(III), Tb(III), Er(III) and Yb(III) Schiff bases. These complexes were characterized using elemental analysis, molar conductivity, Fourier transform infrared and UV–visible spectroscopies, and thermogravimetry–differential thermal analysis. The general formula of the complexes is [Ln(L)(NO₃)₂(H₂O)].NO₃ (L = Schiff base ligand). The spectroscopic data reveal that the Schiff base ligand behaves as a tridentate ligand with ONO donor atoms sequencing towards the central metal ion. An investigation of fluorescence properties of the Sm(III), Er(III) and Tb(III) complexes shows that the Ln(III) ions can be sensitized efficiently by the ligand to some extent. Antimicrobial activity testing indicates that all six complexes exhibit antibacterial and antifungal ability against microbes with broad antimicrobial spectra. In addition, the antioxidant properties of the complexes were also screened. Copyright © 2014 John Wiley & Sons, Ltd.     

Syntheses and crystal structures of four new organotin complexes with Schiff bases containing triazole

Four new organotin complexes, namely [(Bu₂Sn)₂O(EtO)(L1)]₂ (1), [(Bu₂Sn)₂O(EtO)(L2)]₂ (2), [(Bu₂Sn)₂O(EtO)(L3)]₂ (3) and [Ph₃Sn(L4)] · 0.5H₂O (4), were obtained by reactions of Bu₂SnO and Ph₃SnOH with 4-phenylideneamino-3-methyl-1,2,4-triazole-5-thione (HL1), 4-furfuralideneamino-3-methyl-1,2,4-triazole-5-thione (HL2), 4-(2-thienylideneamino)-3-ethyl-1,2,4 -triazole-5-thione (HL3) and 4-(3,5-di-t-butylsalicylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL4). Compounds 1-4 were characterized by elemental analysis, IR spectra and their structures were determined by single-crystal X-ray diffraction methods. Complexes 1-3 show similar structures containing a Sn₄O₄ ladder skeleton in which each of the exo tin atoms is bonded to the N atom of a corresponding thione-form deprotonated ligand. Complex 4 shows a mononuclear structure in which the tin atom of triphenyltin group is coordinated by the S atom of a thiol-form L4⁻ anion.     

The metal complexes of new Schiff bases containing phosphonate groups and catalytic properties for alkane oxidation

In this study, two new salicylidene phosphonate ligands (HL¹ and HL²) and their metal complexes (Cu²⁺, VO²⁺ and La³⁺) were synthesized and characterized by spectroscopic and analytical methods. The molecular structure of the ligand HL¹ was determined by single‐crystal X‐ray diffraction study. In the structure of the ligand, there is an intramolecular phenol‐imine hydrogen bond. The synthesized compounds exhibit only one emission maximum upon excitation at 270–295  nm range. Complexation of the Schiff base ligands with metal ions did not cause a considerable quenching effect. Finally, the complexes prepared were used as catalysts in cyclohexane oxidation under microwave irradiation. The complexes showed high conversion rates (> 90%) for cyclohexane oxidation; however, poor selectivity was observed for all complexes. The La³⁺ complexes showed better selectivity for cyclohexane → cyclohexanol transformation with about 45% selectivity.