Mono- and dinuclear Fe(III) complexes with the N2O2 donor 5-chlorosalicylideneimine ligands; synthesis, X-ray structural characterization and magnetic properties

Two novel monomeric [C₁₈H₁₇Cl₃N₂O₂Fe] (1) and dimeric [C₃₈H₃₆N₄O₄Cl₆Fe₂] (2) Fe(III) tetradentate Schiff base complexes have been synthesized and their crystal structures have been determined by single crystal X-ray diffraction analysis. In complex (1) the Schiff base ligand coordinates toward one iron atom in a tetradentate mode and each iron atom is five coordinated with the coordination geometry around iron atom which can be described as a distorted square pyramid. The presence of a short (2.89 Å) non-bonding interatomic Fe···O distances between adjacent monomeric Fe(III) complexes results in the formation of a dimer. Structural analysis of compound (2) shows that the structure is a centrosymmetric dimer in which the six coordinated Fe(III) atoms are linked by μ-phenoxo bridges from one of the phenolic oxygen atoms of each Schiff base ligand to the opposite metal center. The variable-temperature (2-300 K) magnetic susceptibility (χ) data of these two compounds have been investigated. The results show that for both complexes Fe(III) centers are in the high spin configuration (S = 5/2) and indicate antiferromagnetic spin-exchange interaction between Fe(III) ions. The obtained results are briefly discussed using magnetostructural correlations developed for other class of iron(III) complexes.     

Unusual dinuclear copper(II) and nickel(II) complexes of a novel Schiff base deriving from 2-aminoethanol

It is generally accepted that copper(II) complexes involving 2-aminoethanol or a Schiff base deriving from this aminoalcohol display a tetranuclear structure with a Cu₄O₄ ‘cubane’ core. Using a Schiff base obtained by reacting 2′-aminoacetophenone with 2-aminoethanol, we have prepared copper(II) and nickel(II) complexes whose properties are fully consistent with a dinuclear structure. The copper complex is characterized by a low antiferromagnetic interaction.     

Cd(II) and Cu(II) complexes of polydentate Schiff base ligands: synthesis, characterization, properties and biological activity

We report the synthesis of the Schiff base ligands, 4-[(4-bromo-phenylimino)-methyl]-benzene-1,2,3-triol (A₁), 4-[(3,5-di-tert-butyl-4-hydroxy-phenylimino)-methyl]-benzene-1,2,3-triol (A₂), 3-(p-tolylimino-methyl)-benzene-1,2-diol (A₃), 3-[(4-bromo-phenylimino)-methyl]-benzene-1,2-diol (A₄), and 4-[(3,5-di-tert-butyl-4-hydroxy-phenylimino)-methyl]-benzene-1,3-diol (A₅), and their Cd(II) and Cu(II) metal complexes, stability constants and potentiometric studies. The structure of the ligands and their complexes was investigated using elemental analysis, FT-IR, UV-Vis, ¹H and ¹³C NMR, mass spectra, magnetic susceptibility and conductance measurements. In the complexes, all the ligands behave as bidentate ligands, the oxygen in the ortho position and azomethine nitrogen atoms of the ligands coordinate to the metal ions. The keto-enol tautomeric forms of the Schiff base ligands A₁-A₅ have been investigated in polar and non-polar organic solvents. Antimicrobial activity of the ligands and metal complexes were tested using the disc diffusion method and the strains Bacillus megaterium and Candida tropicalis.Protonation constants of the triol and diol Schiff bases and stability constants of their Cu²⁺ and Cd²⁺ complexes were determined by potentiometric titration method in 50% DMSO-water media at 25.00 ± 0.02 °C under nitrogen atmosphere and ionic strength of 0.1 M sodium perchlorate. It has been observed that all the Schiff base ligands titrated here have two protonation constants. The variation of protonation constant of these compounds was interpreted on the basis of structural effects associated with the substituents. The divalent metal ions of Cu²⁺ and Cd²⁺ form stable 1:2 complexes with Schiff bases.The Schiff base complexes of cadmium inhibit the intense chemiluminescence reaction in dimethylsulfoxide (DMSO) solution between luminol and dioxygen in the presence of a strong base. This effect is significantly correlated with the stability constants K_CdL of the complexes and the protonation constants K_OH of the ligands; it also has a nonsignificant association with antibacterial activity.     

New macrocyclic Schiff-base complexes incorporating a phenanthroline unit. Part 2: Template synthesis of some manganese(II) complexes and crystal structure studies

A series of Mn(II) macrocyclic Schiff-base complexes [MnLⁿ]²⁺ have been prepared via the Mn(II) templated [1+1] cyclocondensation of 2,9-dicarboxaldehyde-1,10-phenanthroline with appropriate linear and branched amines. In this way ligands the pentaaza macrocycle L¹ which is 15-membered and L² which is 16-membered possessing no pendant arm, L⁶ is 15-membered with one 2-aminoethyl pendant arm and L⁸ which is 18-membered hexaaza macrocycle with two 2-aminoethyl pendant arms are formed. All the complexes have been characterized using spectroscopic methods. The crystal structures of [MnL⁸](ClO₄)₂ · EtOH were determined and indicate that in the solid state the complex adopts a slightly distorted hexagonal bipyramid geometry with the Mn(II) ion located within a hexaaza macrocycle with the two pendant amines coordinating in the axial positions.     

Synthesis and characterization of technetium(V) complexes with tridentate schiff base ligands. X-ray crystal structure of chloro[N-(2-hydroxyphenyl)salicylideneiminato]oxotechnetium(V)

Five-coordinate technetium(V) complexes of the form TcO(L)Cl where L is one of the two tridentate Schiff base ligands N-(2-oxidophenyl)salicylideneiminate or N-(2-mercaptophenyl)salicylideneiminate have been synthesized and characterized. These neutral complexes precipitate from methanol upon reaction of the Schiff base ligand with TcOCl₄^?. A single crystal X-ray structure determination shows that the chloro [[N-(2-oxidophenyl)salicylideneiminato](2?)-N,O,O′]oxotechnetium(V) complex, [TcO(C₁₃H₉NO₂)Cl], formula weight 362, has a distorted square pyramidal coordination geometry with the oxo ligand in the axial position. The steric requirements of the oxo group cause the Tc atom to be displayed 0.67 Å out of the mean equatorial plane of the other four donor atoms. This complex crystallizes in the monoclinic space group P2₁/a with a = 13.423(6) Å, b = 12.570(5) Å, c = 7.769(3) Å, β = 106.53(5)°, V = 1256.7(9) ų, and Z = 4. The structure has been refined to R = 0.047 for 1775 observed reflections.     

Surfactant–copper(II) Schiff base complexes: synthesis,structural investigation,DNA interaction,docking studies,and cytotoxic activity

A series of surfactant–copper(II) Schiff base complexes (1–6) of the general formula, [Cu(sal-R₂)₂] and [Cu(5-OMe-sal-R₂)₂], {where, sal?=?salicylaldehyde, 5-OMe-sal?=?5-methoxy- salicylaldehyde, and R₂?=?dodecylamine (DA), tetradecylamine (TA), or cetylamine (CA)} have been synthesized and characterized by spectroscopic, ESI-MS, and elemental analysis methods. For a special reason, the structure of one of the complexes (2) was resolved by single crystal X-ray diffraction analysis and it indicates the presence of a distorted square-planar geometry in the complex. Analysis of the binding of these complexes with DNA has been carried out adapting UV-visible-, fluorescence-, as well as circular dichroism spectroscopic methods and viscosity experiments. The results indicate that the complexes bind via minor groove mode involving the hydrophobic surfactant chain. Increase in the length of the aliphatic chain of the ligands facilitates the binding. Further, molecular docking calculations have been performed to understand the nature as well as order of binding of these complexes with DNA. This docking analysis also suggested that the complexes interact with DNA through the alkyl chain present in the Schiff base ligands via the minor groove. In addition, the cytotoxic property of the surfactant–copper(II) Schiff base complexes have been studied against a breast cancer cell line. All six complexes reduced the visibility of the cells but complexes 2, 3, 5, and 6 brought about this effect at fairly low concentrations. Analyzed further, but a small percentage of cells succumbed to necrosis. Of these complexes (6) proved to be the most efficient aptotoxic agent.     

Lanthanide chelate complexes of salicyloyl hydrazide-salicylaldehyde schiff base (SHSASB) and anthranilic acid-salicylaldehyde schiff base (AASASB)

New lanthanide complexes of salicylaldehyde- Schiff bases with salicyloyl hydrazide and anthranilic acid, were synthesized by a novel method consisting of refluxing the mixtures of Schiff base ligands and lanthanide trichloroacetate in acetone. Solid complexes of formulae Ln(SHSASB)₃·2H₂O and Ln₂(AASASB)₃·2H₂O where Ln = La---Yb and Y, were isolated. Pronto NMR and IR spectra for the complexes reveal the bidentate binding of both the Schiff base ligands to the lanthanide ion. Electronic spectra along with the conductance data for the complexes indicate a coordination number of six for the lanthanide ion in the complexes of both the Schiff bases.     

Proton translocation in hydrogen bonds with large proton polarizability formed between a Schiff base and phenols

OH…N ? O^?…H⁺N hydrogen bonds formed between N-all-transretinylidene butylamine (Schiff base) and phenols (1:1) are studied by IR spectroscopy. It is shown that both proton limiting structures of these hydrogen bonds have the same weight with Δ pK_a (50%) = (pK_a protonated Schiff base minus pK_a phenol) = 5.5. With the largely symmetrical systems, continua demonstrate that these hydrogen bonds show great proton polarizability. In the Schiff base + tyrosine system in a non-polar solvent the residence time of the proton at the tyrosine residue is much larger than that at the Schiff base. In CH₂CCl₂ these hydrogen bonds show, however, still proton polarizability, i.e., the position of the proton transfer equilibrium OH…N ? O^?…H⁺N is shifted to and fro as function of the nature of the environment of this hydrogen bond. Consequences regarding bacteriorhodopsin are discussed.     

Synthesis, characterization and X-ray crystal structures of dinuclear nickel(II) complexes of a novel potentially hexadentate but functionally tetradentate binucleating ligand

A binucleating potentially hexadentate chelating agent containing oxygen, nitrogen and sulfur as potential donor atoms (H₂ONNO) has been synthesized by condensing α,α-xylenebis(N-methyldithiocarbazate) with 2,4-pentanedione. An X-ray crystallographic structure determination shows that the Schiff base remains in its ketoimine tautomeric form with the protons attached to the imine nitrogen atoms. The reaction of the Schiff base with nickel(II) acetate in a 1:1 stoichiometry leads to the formation of a dinuclear nickel(II) complex [Ni(ONNO)]₂ (ONNO²⁻ = dianionic form of the Schiff base) containing N,O-chelated tetradentate ligands, the sulfur donors remaining uncoordinated. A single crystal X-ray structure determination of this dimer reveals that each ligand binds two low spin nickel(II) ions, bridged by a xylyl group. The nickel(II) atoms adopt a distorted square-planar geometry in a trans-N₂O₂ donor environment. Reaction of the Schiff base with nickel(II) acetate in the presence of excess pyridine leads to the formation of a similar dinuclear complex, [Ni(ONNO)(py)]₂, but in this case comprises five coordinate high-spin Ni(II) ions with pyridine ligands occupying the axial coordination sites as revealed by X-ray crystallographic analysis.     

Isolation of a novel intermediate during unsymmetrical to symmetrical rearrangement of a tetradentate Schiff base ligand in a manganese(III) complex: Catalytic activity of the rearranged product towards alkene epoxidation

An attempt for the synthesis of a Mn^III complex with unsymmetrical tetradentate Schiff base ligand uspen (1:1:1 condensate of salicylaldehyde, 2,4-pentanedione and 1,2-ethanediamine) resulted in the isolation of a novel complex, {[{Mn(salen)}{Mn(uspen)}(HCOO)]·ClO₄}_n (1) as an intermediate species that contains both the unsymmetrical and symmetrical tetradentate ligand uspen and salen (2:1 condensate of salicylaldehyde and 1,2-ethanediamine) respectively. The structure of the complex shows that half of the unsymmetrical Schiff base, uspen rearranged to its symmetrical analogue, salen. A phenoxo bridged dinuclear Mn^III complex [Mn(salen)(sal)]₂·2H₂O (2) with only the symmetrical Schiff base was also obtained. Compound 1 that contains both unsymmetrical and symmetrical Schiff base ligands in one molecule is unprecedented and provides an insight into the unsymmetrical to symmetrical rearrangement of tetradentate Schiff base ligand. Complex 2 acts as an efficient catalyst in the alkene ((E)-stilbene, styrene) epoxidation reaction in presence of two terminal oxidants PhIO and NaOCl in solvents CH₃CN and CH₂Cl₂ independently and it retains its reactivity with high efficiency for a long time.     

The chromophore-binding site of bacteriorhodopsin. Resonance Raman and surface-enhanced resonance Raman spectroscopy and quantum chemical study

Surface-enhanced Raman spectra of membrane protein, located in native mem brane, bacteriorhodopsin, adsorbed by silver electrodes and hydrosols have been obtained for the first time. The distance between the retinal Schiff’s base and the external side of purple membrane of Halobacteriim halobiim was shown to be 6–9 A. The possible distribition of the point charges aroind protonated retinal Schiff’s base has been proposed on the basis of the resonance Raman data and quantim chemical CNDO/S-CI calculations. Such a model contains tyrosine residue located near the retinal Schiff’s base and connected with COO^- groipvia hydrogen bond COO^- group acts as a protonated Schiff’s base counterion. The distance between oxygen atoms of COO^- group and retinal Schiff’s base plane is 2.5–3.0A. The hydrogen bond (O-H. . .O^-) length between oxygen atom of OH-group and oxygen atom of COO^- group has been chosen 2.7±0.1Å Tyrosine hydroxyl group is located at 2.8–3.5 A from retinal Schiff’s base plane. It was shown that in contrast to generally accepted Honig and Nakanishi model the spectral properties of Brh570, K610, L550 and M4Ï2 forms of bacteriorhodopsin photocycle as well as observed tyrosine deprotonation and COO^- group protonation during M412 formation can be explained reasonably well by the suggested charge distribution. Furthermore, such a model of bacteriorhodopsin active site microenvironment allows to explain catalyzing of photo-induced protonated retinal Schiff’s base deprotonation observed in our preliminary experiments.     

Mononuclear Ni(II) and Zn(II) complexes of some potentially binucleating Schiff base ligands

Mononuclear Zn(II) and Ni(II) complexes have been prepared from two new Schiff base ligands in which two alternative co-ordination sites (N₂O₂ or O₂O₂) occur. The first ligands is the Schiff base derived from 1,2-diaminobenzene and 2-hydroxy-3-carboxyl-1-napthaldehyde (bopaH₄). The complexes of this ligand contain the metal ions in the N₂O₂ coordination site as a result of the steric requirements of the co-ordinated ligand. The second ligand series are derivatives of X-substituted 1,2-diaminobenzenes, 2-hydroxy-3-carboxy-1-naphthaldehyde and 2-hydroxy-5-methyl isophthaldehyde (X-bolaH₃). In this case Ni(II) occupies the N₂O₂ site in its complexes with the X-bolaH₃ ligands, whereas the Zn(II) complexes are co-ordinate through the O₂O₂ site since the steric restrictions are less severe.     

Unexpected isomeric equilibrium in pyridoxamine Schiff bases

Pyridoxamine is a vitamin B₆ derivative involved in biological reactions such as transamination, and can also act as inhibitor in protein glycation. In both cases, it has been reported that Schiff base formation between pyridoxamine and carbonyl compounds is the main step. Nevertheless, few studies on the Schiff base formation have been reported to date. In this work, we conduct a comparative study of the reaction of pyridoxamine and 4-picolylamin (a pyridoxamine analog) with various carbonyl compounds including propanal, formaldehyde and pyruvic acid. Based on the results, 4-picolylamin forms a Schiff base as end-product of its reactions with propanal and pyruvic acid, but a carbinolamine with formaldehyde. On the other hand, pyridoxamine forms a Schiff base with the three reagents, but the end-product is in equilibrium with its hemiaminal form, which results from the attack of the phenolate ion of the pyridine ring on the imine carbon. This isomeric equilibrium should be considered in studying reactions involving amine derivatives of vitamin B₆.     

Electrochemical synthesis and crystal structure of iron(II), cobalt(II), nickel(II) and copper(II) complexes of dianionic tetradentate N4 Schiff base ligand

The electrochemical oxidation of anodic metal (iron, cobalt, nickel and copper) in an acetonitrile solution of the potentially chelating Schiff base N,N(dithiodiethylenebis-(aminylydenemethylydene)-bis(1,2-phenylene)ditosylamide (H₂L) afforded stable complexes of empirical formula [ML]. The compounds obtained have been characterized by microanalysis, IR spectroscopy and ES-MS mass spectrometry. The crystal and molecular structures of [FeL]·CH₃CN (1) [CoL]·CH₃CN (2), [NiL]·CH₃CN (3) and [CuL]·CH₃CN (4) have been determined by X-ray diffraction in all complexes, the metal atom is in a distorted tetrahedral environment with the Schiff base acting as a tetradentate N4 donor.     

Coordination chemistry of two new tetraaza Ni(II) and Cu(II) macrocyclic and two new Co(II) and Zn(II) macroacyclic Schiff base complexes containing piperazine moiety: X-ray crystal structures of Ni(II) and Zn(II) complexes

A new potentially tetradentate (N₄) Schiff base ligand (L), 1,9,12,20-tetraazatetracyclo[18.2.2.02,7.014,19]tetracosa-2(7),3,5,8,12,14(19),15,17-octaene containing a piperazine moiety is described. Macrocyclic Schiff base complexes, [NiL](ClO₄)₂ (1) and [CuL](ClO₄)₂ (2) have been obtained from equimolar amounts of ligand (L) with nickel(II) and copper(II) metal ions. While the equilibrium reaction in the presence of cobalt(II) and zinc(II) metal ions with ligand L in a 1:1 molar ratio yielded the open-chain Schiff base complexes, [CoL′](ClO₄)₂ (3) and [ZnL′](ClO₄)₂ (4) containing two terminal primary amino groups. The ligand L′ is 1,4-bis(2-(2-aminoethyliminomethyl)phenyl)piperazine. The crystal structures of (1) and (4) have been also determined by X-ray diffraction. It was shown that the Ni(II) is coordinated to the ligand L by two nitrogen atoms of piperazine group and two nitrogen atoms of the imine groups, in a slightly distorted square-planar geometry. Also single crystal X-ray analysis of (4) confirmed a distorted octahedral arrangement in the vicinity of Zn atom with N₆ donor set. The spectroscopic characterization of all complexes is consistent with their crystal structures.     

Synthesis,Physico-Chemical investigations of Co(II), Ni(II) and Cu(II) complexes and their in vitro microbial,cytotoxic, DNA cleavage studies

A series of metal complexes of cobalt(II), nickel(II), and copper(II) have been synthesized with newly derived biologically active ligands. These ligands were synthesized by the condensation of 2-amino-4-phenyl-1,3-thiazole with 8-formyl-7-hydroxy- 4-methylcoumarin. The probable structure of the complexes has been proposed on the basis of analytical and spectroscopic data (IR, UV-Vis, ESR, FAB-mass, and thermoanalytical). Electrochemical study of the complexes is also reported. Elemental analysis of the complexes confined them to stoichiometry of the type ML₂.2H₂O [M = Co(II), Ni(II), and Cu(II)]. The Schiff base and its metal(II) complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Staphylococcus pyogenes, and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Aspergillus flavus, and Cladosporium) by the MIC method. The brine shrimp bioassay was carried out to study their in vitro cytotoxic properties, and also the Schiff base and its metal(II) complexes have been studied for DNA cleavage.     

Stability of Schiff bases of amino acids and pyridoxal-5′-phosphate

Summary Stability of Schiff bases from Pyridoxal-5-phosphate and- and non-amino acids and amines have been studied in a wide range of pH. Furthermore the transamination process for the PLP-serine Schiff base and the cyclization reaction of PLP-histidine Schiff base have also been studied.Results show that the-position on carboxyl group of amino acids plays an important role on the mechanism of hydrolysis of imine bond. Absence of ionic groups in the surroundings of that bond seems to be an important fact of stability.In the transamination reaction, the rate-determining step is the isomerization of the Schiff base to ketoimine, since the rate constants for disappearance of Schiff base coincide with the rate constants for PMP formation. This process is catalyzed by the OH^–/H₂O system and the monoprotonated amino acid.     

Assessment of biological activities of chitosan Schiff base tagged with medicinal plants

A chitosan Schiff base with an aromatic aldehyde was synthesized and characterized by FTIR and NMR spectroscopies. Furthermore, the degree of substitution was calculated based on the ratios of the area of the proton of the imine (A_imine) and the area of the peak of the proton of the pyranose ring (A_H-2). The antimicrobial activities were determined against bacterial and fungal strains, as well as multiple drug-resistant (MDR) bacteria. The chitosan Schiff base was also tagged with medicinal plants, for example, Curcuma longa, Peganum harmala, Lepidium sativam, and cruciferous vegetables, and the biological activities determined against pathogenic bacterial and fungal strains. The chitosan Schiff base showed maximum zone of inhibition of 22 mm against Staphylococcus aureus with a minimum zone of inhibition of 15 mm against Bacillus cereus. The chitosan Schiff base was fused with C longa, isothiocyanates and a combined mixture of P harmala and L sativam that has shown activities against Escherichia coli with a zone of inhibition of 28, 24, and 30 mm, respectively. The Schiff base of chitosan fused with medicinal plants also showed significant inhibitory activities against MDR bacteria.     

Magnetic, spectroscopic and X-ray crystallographic structural studies on copper(II) complexes of tridentate NNS Schiff base ligands formed from 2-acetylpyrazine and S-methyl- and S-benzyldithiocarbazates

New copper(II) complexes of general empirical formula, [Cu(NNS)X] (NNS = anionic forms of the 2-acetylpyrazine Schiff bases of S-methyl- and S-benzyldithiocarbazate, Hapsme and Hapsbz) and X = Cl⁻, Br⁻, NCS⁻ and NO₃⁻ have been synthesized and characterized. X-ray crystal structures of the free ligand, Hapsbz and the complexes, [Cu(apsbz)(NO₃)]_∞, [Cu(apsme)(NCS)]₂ and [Cu(apsme)Cl]₂ have been determined. In the solid state, the Schiff base, Hapsbz remains in its thione tautomeric form with the thione sulfur atom trans to the azomethine nitrogen atom. X-ray diffraction shows that the [Cu(apsbz)(NO₃)]_∞ complex is a novel coordination polymer in which one of the nitrogen atoms of the pyrazine ring bridges two adjacent copper(II) ions. The Schiff base is coordinated to the copper(II) ion in its iminothiolate form via the thiolate sulfur atom, the azomethine nitrogen atom and one of the pyrazine nitrogen atoms, the overall geometry of each copper atom in the polymer being close to a square-pyramid. The complexes, [Cu(apsme)X]₂ (X = NCS⁻, Cl⁻) are dimers in which each copper atom adopts a five-coordinate near square-pyramidal geometry with an N₃S₂ coordination environment. The Schiff base coordinates as a uninegatively charged tridentate ligand chelating via the pyridine and azomethine nitrogen atoms and the thiolate sulfur atoms. A nitrogen atom of a unidentate thiocayanate or chloride ligand and a bridging sulfur atom from a second ligand completes the coordination sphere. Room temperature μ_eff values for the complexes in the solid state are in the range 1.70-2.0 μ_B typical of uncoupled or weakly coupled Cu(II) centres. Variable temperature susceptibility studies show that the chain complex displays weak ferromagnetic coupling across the pyrazine bridges, while the S-bridged dinuclear compounds display either weak ferromagnetic or weak antiferromagnetic coupling that relates to subtle bridging geometry differences. EPR studies of frozen DMF solutions give rather similar g and A_Cu values for all compounds indicative of Cu(d_x²-y²) ground state orbitals on the Cu centers.     

Resonance Raman study of intermediates of the halorhodopsin photocycle

The resonance Raman (RR) study of the retinal protein halorhodopsin (HR₅₇₈) was extended to two of its photoproducts: HR and HR^L₄₁₀ RR spectra of both species were recorded in H₂O and D₂O and compared with the RR spectra of the intermediates L₅₅₀ and M₄₁₂ from the bacteriorhodopsin photocycle. HR₅₂₀ was found to be a protonated Schiff base in the 13-cis configuration and HR^L₄₁₀ a deprotonated Schiff base in the 13-cis configuration.