Synthesis,Characterization and Antifungal Activity of Metal Complexes of 2-(5-((2-Chlorophenyl)Diazenyl)-2-Hydroxybenzylidene) Hydrazinecarbothioamide

Abstract

New metal complexes of Co(II), Cu(II), Ni(II), Zn(II), Mn(II), Fe(III), Ru(III), UO₂(II), and VO(II) with the Schiff base, 2-(5-((2-chlorophenyl)diazenyl)-2-hydroxy- benzylidene) hydrazine-carbothioamide (H₂L) have been prepared and characterized by elemental and thermal analyses, FT-IR, UV–Vis, mass spectra, ¹H-NMR, and ESR as well as conductivity and magnetic moments measurements. The IR spectra showed that the ligand acts as neutral tridentate, neutral bidentate or monobasic tridentate ligand. The geometries of metal complexes were either octahedral or square pyramidal. The ESR spectra of the solid copper(II) complexes indicated an axial symmetry type of a d_(x2-y2) ground state with considerably ionic or covalent environment. The effect of the presence of an azo group on the biological activity of the ligand was investigated. The ligand and its complexes are biologically inactive due to the presence of azo group.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

Synthesis,Spectroscopic and Magnetic Studies on Metal Complexes of 5-Methyl-3-(2-Hydroxyphenyl)Pyrazole

A tridentate ONN donor ligand, 5-methyl-3-(2-hydroxyphenyl)pyrazole; H₂L, was synthesized by reaction of 2-(3-ketobutanoyl)phenol with hydrazine hydrate. The ligand was characterized by IR, ¹H NMR and mass spectra. ¹H NMR spectra indicated the presence of the phenolic OH group and the imine NH group of the heterocyclic moiety. Different types of mononuclear metal complexes of the following formulae [(HL)₂M][sdot]xH₂O (M=VO, Co, Ni, Cu, Zn and Cd), [(HL)₂M(H₂O)₂] (M=Mn and UO₂) and [(HL)LFe(H₂O)₂] were obtained. The Fe(III) complex, [(HL)LFe(H₂O)₂] undergoes solvatochromism. Elemental analyses, IR, electronic and ESR spectra as well as thermal, conductivity and magnetic susceptibility measurements were used to elucidate the structures of the newly prepared metal complexes. A square-pyramidal geometry is suggested for the VO(IV) complex, square-planar for the Cu(II), Co(II) and Ni(II) complexes, octahedral for the Fe(III) and Mn(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes, while the UO₂(VI) complex is eight-coordinate. Transmetallation of the UO₂(VI) ion in its mononuclear complex by Fe(III), Ni(II) or Cu(II) ions occurred and mononuclear Fe(III), Ni(II) and Cu(II) complexes were obtained. IR spectra of the products did not have the characteristic UO₂ absorption band and the electronic spectra showed absorption bands similar to those obtained for the corresponding mononuclear complexes. Also, transmetallation of the Ni(II) ion in its mononuclear complex by Fe(III) has occurred. The antifungal activity of the ligand and the mononuclear complexes were investigated.     

Mandelazo I As A Reagent For Zr(IV) Determination

Abstract

A spectromeric study of the reaction of the Zr(IV) ions with Mandelazo I was carried out. Absorption spectra revealed that the maximum absorption of the zirconium compound appears at a wavelength (316 nm) different from the maxima of the reagent (253 and 390 nm). Beer-Lambert law is followed for zirconium concentrations of the order of 8.8x 10^?5 M (i.e. 8 μg Zr (IV)/mL). Possible interferences of ions such as Be(II), Cu(II), Zn(II), Al(III), Th(IV), U(VI), Mn(II), Fe(III), Co(II) and Ni(II) were investigated in connection with some masking agents such as SO₄ ^2- and C₂O₄ ^2-. Also, the solid state Zr(IV)-Mandelazo I compound was prepared and characterized by nitrogen and thermogravimetric analyses.     

Spectrometric Studies on the Complexation of Pd(II), Fe(III) and Pt(IV) with mandelazo I

Abstract

A spectrometric study of the reaction between Pd(II), Fe(III) and Pt(IV) ions, and Mandelazo I was carried out. The optimum conditions favouring the formation of the complexes are extensively investigated. The stoichiometry of the complexes formed in solution (1:2, 1:1, 1:1), their apparent stability constants (5.45 × 10⁹, 2.39 × 10⁶, 4.12 × 10⁵) and the ranges for obedience to beer's law (0.2 – 6.4, 0.25 – 7.0, 1.5 – 42.0 μg/mL) are reported for Pd(II), Fe(III) and Pt(IV), respectively. The effect of some metal ions including Cu(II), Zn(II), Mn(II), Cd(II), Hg(II), Co(II), Ni(II), Be(II), Al(III), Th(IV) and U(VI), on the maximum absorbance of the formed complexes was also investigated.     

Synthesis,characterization and susceptibility of bacteria against Sulfamethoxydiazine complexes of copper(II), zinc(II), nickel(II), cadmium(II), chromium(III) and iron(III)

Complexes of sulfamethoxydiazine with Cu(II), Zn(II), Ni(II), Cd(II), Cr(III) and Fe(III) have been synthesized and characterized on the basis of conductivity measurements, elemental analyses, UV, IR, ¹H?NMR and thermal studies. It is shown that sulfamethoxydiazine behaves as a bidentate ligand, binding the metal ion through the sulfonyl oxygen and sulfonamide nitrogen. In vitro susceptibility tests of these complexes against Escherichia coli, Bacillus subtilis, Proteus vulgaris and Staphylococcus aureus were carried out. The results show that the antibacterial activities of the complexes of Zn(II), Cu(II), Cr(III) and Fe(III) are, in general, stronger than that of sulfamethoxydiazine, while the complexes of Cd(II) and Ni(II) are less active.     

A selective chemosensor for detection of Ag(I) and Cu(I) based on an acenaphthoquinone derivative and its complexes

A new Schiff base, acenaphthoquinone bis(diphenylmethlenehydrazone) (L), was synthesized and employed as a chemosensor for detecting Ag(I) and Cu(I). Experimental results showed that the chemosensor exhibited high selectivity and sensitivity. The sensitivity of the chemosensor for Ag(I) or Cu(I) was not affected by other metal ions, such as Ni(II), Nd(III), Zn(II), Fe(III), Cu(II), Na(I), La(III), K(I), and Co(II). Complexes 1 and 2 were synthesized by coordination of L with Ag(I) and Cu(I), respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. They had the same space group P2₁/c. Based on theoretical calculation, mechanism of the chemosensor detecting Ag(I) and Cu(I) was suggested.     

A NEW CYCLOBUTANE SUBSTITUTED SCHIFF BASE LIGAND,SYNTHESIS OF ITS Cd(II), Co(II), Cu(II), Ni(II) AND Zn(II) COMPLEXES AND INVESTIGATION OF THEIR STRUCTURE

Abstract

A new, thiazole derivative ligand, 4-(1-phenyl-1-methylcyclobutane-3-yl)-2-(2-hydroxy-5-bromo benzylidenehydrazino) thiazole (LH), has been synthesized by the reaction of 2-hydroxy-5-bromobenzaldehyde, thiosemicarbazide and subsequently 1-phenyl-1-methyl-3-(2-chloro-1-oxoethyl) cyclobutane. Mononuclear complexes with a metal-ligand ratio of 1 : 2 have been prepared with Cd(II), Co(II), Cu(II), Ni(II) and Zn(II). The authenticity of the ligand and its complexes was established by elemental analyses, IR, ¹³C and ¹H NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC).     

A thermal behaviour and structural study of bis(hydroxamato)oxovanadium(IV) complexes

The bis(hydroxamato)oxovanadium(IV) complexes of composition [VO(IAH)₂)] (I), [VO(IBH)₂)] (II) and [VO(ICH)₂)] (III) (where IAH = indole-3-acetohydroxamate; (C₉H₈NCONHO^?); IBH = indole-3-butyrohydroxamate; (C₁₁H₁₂NCONHO^?); ICH = indole-2-carbohydroxamate; (C₈H₆NCONHO^?)) synthesized form the reactions of VOSO₄·5H₂O with bi-molar amounts of potassium salts of the respective hydroxamic acids in methanol have been characterised by elemental analyses, magnetic moment measurements and IR spectral studies. The thermal behaviour of complexes has been studied by TG and DTA techniques. Thermograms indicated that all complexes decompose in two steps yielding [VO(IAH)], [VO(IBH)] and [VO(ICH)] as intermediate of respective complexes and VO₂ as the final product of decomposition in each case. From the initial decomposition temperatures (IDT), the order of thermal stability for the complexes has been inferred as II > I > III.     

SYNTHESIS AND CHARACTERIZATION OF Fe(III), Co(III), Cu(II) AND Zn(II) COMPLEXES OF N-2,4-HYDROXYBENZAL-D-GLUCOSAMINE

Abstract

The Schiff base N-2,4-dihydroxybenzal-D-glucosamine (L), and its Fe(III), Co(III), Cu(II) and Zn(II) complexes have been synthesized and characterized. Magnetic moments suggest that all complexes are high-spin. The Cu(II) chelate in DMF solution has a distorted tetrahedral structure, as shown by ESR and electronic spectra. Detailed studies have been made concerning the solution equilibrium of L with transition metal ions. Stabilities of the complexes are in accord with the Irving-Williams series.     

Hg(II), Tl(III), Cu(I), and Pd(II) Complexes with 2,2'-Diphenyl-4,4'-Bithiazole (DPBTZ), Syntheses and X-Ray Crystal Structure of [Hg(DPBTZ)(SCN)2]

Reaction of the ligand 2,2′-diphenyl-4,4′-bithiazole (DPBTZ) with Hg(SCN)₂, Tl(NO₃)₃, CuCl, and PdCl₂ gives complexes with stoichiometry [Hg(DPBTZ)(SCN)₂], [Tl(DPBTZ)(NO₃)₃], [Cu(DPBTZ)(H₂O)Cl]_, and [Pd(DPBTZ)Cl₂]. The new complexes were characterized by elemental analyses and infrared spectroscopy. The crystal structure of [Hg(DPBTZ)(SCN)₂] determined by X-ray crystallography. The Hg atom in the title monomeric complex, (2,2′-diphenyl-4,4′-bithiazole)mercury(II)bisthiocyanate, [Hg(C₁₈H₁₂N₂S₂)(SCN)₂], is four-coordinate having an irregular tetrahedral geometry composed of two S atoms of thiocyanate ions [Hg-S 2.4025(15) and 2.4073(15) Å] and two N atoms of 2,2′-diphenyl-4,4′-bithiazole ligand [Hg-N 2.411(4) and 2.459(4) Å]. The bond angle S(3)-Hg(1)-S(4) of 147.46(5)° has the greatest derivation from ideal tetrahedral geometry. Intermolecular interaction between Hg(1) and two S atoms of two neighboring molecules, 3.9318(15) and 3.9640(18) Å, make the Hg(1) distort from a tetrahedron to a disordered octahedron. The attempts for preparation complexes of Tl(I), Pb(II), Bi(III), Cd(II) ions with 2,2′-diphenyl-4,4′-bithiazole ligand were not successful and also the attempts for preparation complexes of 4,4′,5,5′-tetraphenyl-2,2′-bithizole ligand with Cu(II), Ni(II), Co(II), Co(III), Mn(II), Mn(III), Fe(II), Fe(III), Cr(III), Zn(II), Tl(III), Pb(II), Hg(II), Cu(I), Pd(II) were not successful. This point can be regarded as the initial electron withdrawing of phenyl rings and also their spatial steric effects.     

Green and efficient oxidation of benzylic alcohols with hydrogen peroxide catalyzed by an inorganic–organic hybrid catalyst

Inorganic–organic hybrid catalysts 1-POM(M) were prepared by electrostatic interaction between transition metal-substituted polyoxometalates, {[PW₁₁MO₃₉]^4? [M?=?Cr(III), Fe(III)], [PW₁₁MO₃₉]^5?, [M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II)], [PW₁₁VO₄₀]^4?}, and branched organic polyammonium, (tris[2-(dimethylammonium)ethyl]-1,3,5-benzenetricarboxylate), and characterized by elemental analyses, UV–vis and FT IR spectroscopic techniques, XRD, SEM, and Thermogravimetric-Differential thermogravimetric analyses. The hybrid material 1-POM(Zn) was an efficient and selective heterogeneous catalyst in the oxidation of benzylic alcohols to their corresponding carbonyl compounds with hydrogen peroxide. The catalyst was reused several times without significant loss of catalytic activity.     

One-dimensional zinc(II) fumarate coordination polymers

A new procedure developed for the synthesis and crystallization of various zinc(II) fumarate hydrate coordination polymers is described. In the first step, anhydrous Zn(II) fumarate, [Zn(C₄H₂O₄)] (1), is synthesized from Zn(II) acetate and fumaric acid in methanol. Subsequently, this product is used as a starting material for growing small crystals of bis–aqua Zn(II) fumarate, [Zn(H₂O)₂(C₄H₂O₄)] (2), triaqua Zn(II) fumarate monohydrate, [Zn(H₂O)₃(C₄H₂O₄)]·H₂O (3), tetraaqua Zn(II) fumarate, [Zn(H₂O)₄(C₄H₂O₄)] (4), and tetraaqua Zn(II) fumarate monohydrate, [Zn(H₂O)₄(C₄H₂O₄)]·H₂O (5). All structures were determined or redetermined by X-ray structure analyses. The hitherto unknown compound 3 exhibits a zig-zag chain structure with five-coordinate Zn(II) ions.     

Determination of Metal Ions in Natural Waters by Flame-AAS after Preconcentration on a 5-Amino-1,3,4-Thiadiazole-2-Thiol Modified Silica Gel.

ABSTRACT

5-amino-1,3,4-thiadiazole-2-thiol groups attached on a silica gel surface have been used for adsorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) from aqueous solutions. The adsorption capacities for each metal ion were (in mmol.g^?1): Cd(II)= 0.35, Co(II)= 0.10, Cu(II)= 0.15, Fe(III)= 0.20, Hg(II)= 0.46, Ni(II)= 0.16, Pb(II)= 0.13 and Zn(II)= 0.15. The modified silica gel was applied in the preconcentration and quantification of trace level metal ions present in water samples (river, and bog water).     

Thermoanalytical studies of oxovanadium(IV)hydroxamate complexes

The thermal decomposition behavior of oxovanadium(IV)hydroxamate complexes of composition [VO(acac)(C₆H₅C(O)NHO)] (I), [VO(C₆H₅C(O)NHO)₂] (II), [VO(acac)(4-ClC₆H₄C(O)NHO)] (III), [VO(4-ClC₆H₄C(O)NHO)₂] (IV) (where acac = (CH₃COCHCOCH₃ ^–) synthesized from the reactions of VO(acac)₂ with equi- and bimolar amounts of potassium benzohydroxamate and potassium 4-chlorobenzohydroxamate in THF + MeOH solvent medium has been studied by TG and DTA techniques. TG curves indicated that complexes I, II, and IV undergo decomposition in single step to yield VO₂ as the final residue, while complex III decomposes in two steps to yield VO(acac) as the likely intermediate and VO₂ as the ultimate product of decomposition. The formation of VO₂ has been authenticated by IR and XRD studies. From the initial decomposition temperatures, the order of thermal stability for the complexes has been inferred as IV > I > III > II.     

Synthesis,characterization, and biological activity of metal complexes of azohydrazone ligand

A new azohydrazone, 2-hydroxy-N′-2-hydroxy-5-(phenyldiazenyl)benzohydrazide (H₃L) and its copper(II), nickel(II), cobalt(II), manganese(II), zinc(II), cadmium(II), mercury(II), vanadyl(II), uranyl(II), iron(III), and ruthenium(III) complexes have been prepared and characterized by elemental and thermal analyses as well as spectroscopic techniques (¹H-NMR, IR, UV-Vis, ESR), magnetic, and conductivity measurements. Spectral data showed a neutral bidentate, monobasic bidentate, monobasic tridentate, and dibasic tridentate bonding to metal ions via the carbonyl oxygen in ketonic or enolic form, azomethine nitrogen, and/or deprotonated phenolic hydroxyl oxygen. ESR spectra of solid vanadyl(II) complex (2), copper(II) complexes (3–5), and (7) and manganese(II) complex (10) at room temperature show isotropic spectra, while copper(II) complex (6) shows axial symmetry with covalent character. Biological results show that the ligand is biologically inactive but the complexes exhibit mild effect on Gram positive bacteria (Bacillus subtilis), some octahedral complexes exhibit moderate effect on Gram negative bacteria (Escherichia coli), and VO(II), Cd(II), UO(II), and Hg(II) complexes show higher effect on Fungus (Aspergillus niger). When compared to previous results, metal complexes of this hydrazone have a mild effect on microorganisms due to the presence of the azo group.     

Polyethyleneimine Methylenephosphonic Acid for the Solid-Phase Sorption of Lead(II)

Abstract

In the first part of this work, polyethyleneimine methylenephosphonic acid (PEIMPA) was used as an effective sorbent for solid-phase extraction of Pb(II) ions from an aqueous solution. Conditions for effective sorption are optimized with respect to different experimental parameters in a batch process. The results showed that the amount of extraction decreases with solution pH in the range between 3.5 and 5.8. The sorption capacity is 609 mg·g^?1. The second part of the study focuses on the recovery of Pb(II) from a synthesized binary solution of Pb(II)–Zn(II) and from real Zn(II)-electrolyzed wastewaters. The presence of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), and Zn(II) in large concentrations has a significantly negative effect on extraction properties.     

Synthesis,characterization and antimicrobial activity of homodinuclear complexes derived from 2,6- bis [3′-methyl- 2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol,an end-off compartmental ligand

End-off compartmental pentadentate Schiff base, 2,6-bis[3′-methyl-2′-carboxamidyliminomethyl(6′,7′)benzindole]-4-methylphenol is synthesized and characterized by 2D NMR experiments and mass spectral techniques. The homodinuclear phenalato bridged end-off compartmental Schiff-base complexes Cu(II), Co(II), Ni(II), Mn(II), Fe(III), VO(IV), Zn(II), Cd(II) and Hg(II) have been prepared by the template method using the precursors 2,6-diformyl-4-methylphenol, 3-methyl(6′,7′)-2-benzindolehydrazide and metal chlorides in 1?:?2?:?2 ratio. The complexes are characterized by IR, NMR, UV-vis, FAB-mass, ESR and TGA techniques. Ni(II), Mn(II) and Fe(III) complexes have octahedral geometry, whereas the Cu(II), Co(II), VO(IV), Zn(II), Cd(II) and Hg(II) complexes have square pyramidal geometry. Low magnetic moment values for Cu(II), Co(II), Ni(II), Mn(II), Fe(III) and VO(IV) complexes indicate antiferromagnetic spin-exchange interaction between two metal centers. The metal complexes have been screened for their antibacterial activity against Escherichia coli and Staphyloccocus aureus and antifungal activity against Aspergillus niger and Fusarium oxysporum.     

Synthesis and structural studies of 2-acetylthiophene-2-thenoylhydrazone complexes of oxovanadium(IV), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II)

Complexes with chemical compositions VO(Hatth)₂SO₄, VO(Hatth)₂SO₄·py, [M(Hatth)₂Cl·H₂O]Cl [M = Mn(II), Co(II) and Ni(II)], [Cu(Hatth)₂Cl]₂Cl₂, [Cu(Hatth)₂· Cl·py]Cl, [Cd(Hatth)₂Cl]Cl, M(Hatth)₂Cl₂ [M = Zn(II) and Hg(II)], VO(atth)₂, VO(atth)₂py, M(atth)₂(py)₂ [M = Mn(II) and Cu(II)], M(atth)₂(H₂O)₂ [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)], Hatth = 2-acetylthiophene-2-thenoylhydrazone, and atth, its deprotonated form, have been prepared and characterized by analytical data, molar conductance, magnetic susceptibility, electronic and photoacoustic, ESR, IR and NMR spectral studies. X-ray diffraction study has been used to determine the shape and the dimensions of the unit lattice of copper(II) complexes.     

Determination of Cu(II), Fe(III), Mn(II) and Zn(II) in various samples after preconcentration with Rhizopus oryzae loaded natural cellulose (almond bark)

A procedure for the pre-concentration of Cu(II), Fe(III), Mn(II) and Zn(II) is described utilising a minicolumn of natural cellulose (almond bark) modified with fungus (Rhizopus oryzae) prior to their determination by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). The optimum pre-concentration conditions such as pH and flow rate for the analytes have been investigated. The analytes were quantitatively retained on the column between pH 6 and 8. Elution was made with 10 mL 1 M HCl solution. Under the optimum conditions, recoveries were found as 97 ± 3%, 96 ± 3%, 98 ± 3% and 94 ± 2% for Cu(II), Fe(III), Mn(II) and Zn(II), respectively, at 95% confidence level. The detection limits obtained from preconcentration of 50 mL of blank solutions (n = 11) were 1.6, 1.8, 2.8 and 1.2 µg L^?1 for Cu(II), Fe(III), Mn(II) and Zn(II), respectively. Relative standard deviations (RSD) of the recoveries for five replicate analyses were lower than 3%. The proposed method was validated by analysing certified reference materials (Peach Leaves SRM 1547 and Fish Tissue IAEA-407). Determination of the Cu(II), Fe(III), Mn(II) and Zn(II) in K?z?l?rmak River water, green beans, beans leave and tomato leaves and fish (Tinca tinca) tissue samples was performed by the proposed method.     

Liquid-state mercury(II) ion-selective electrode based on N-(O,O-diisopropylthiophosphoryl)thiobenzamide

A liquid ion-exchange electrode containing a complex of mercury(II) with N-(O,O-diisopropylthiophosphoryl)thiobenzamide in carbon tetrachloride is described. The electrode shows excellent sensitivity and good selectivity. The slope of the calibration graph is 29.0 mV/pHg²⁺ in the pHg²⁺ in the pHg²⁺ range 2–15.2 in mercury(II) ion buffers. The electrode can be used for determination of 5 × 10^?5–10^?2 M Hg(II) in the presence of 10^?2 M Cu(II), Ni(II), Co(II), Zn(II), Pb(II), Cd(II), Mn(II), Fe(III), Cr(III), Bi(III) or Al(III) ions and in the presence of 10^?3 M Ag(I) ions. It can bealso used for end-point detection in titrations with EDTA of 10^?3–10^?4 M mercury(II) at pH 2.