The ring‐opening polymerization of D,L‐lactide catalyzed by new complexes of Cu,Zn, Co,and Ni Schiff base derived from salicylidene and L‐aspartic acid

D ,L ‐lactide (LA) was first successfully ring‐opening polymerized in melt by Schiff base complexes K[ML]nH₂O [M = Cu(II), Zn(II), Co(II), Ni(II); n = 2, 2, 3, 3.5; H₃L = L‐aspartic acid‐salicylidene Schiff base], which were prepared by Schiff base ligand derived from salicylidene and L‐aspartic acid and corresponding acetates. The effects of various complexes, the molar ratio of K[ML]nH₂O/LA, the polymerization temperature, and time were studied in detail. The results show that all complexes studied have the ability to initiate the ring‐opening polymerization of D ,L ‐lactide in melt. More than 90% high polymerization conversion and narrow molecular weight distribution (MWD) can be obtained very easily. However, the Ni(II) complex shows better catalytic property than other complexes on the polymerization and the molecular weight (MW) of poly(D ,L ‐lactide) (PLA) produced. With a rise in temperature and a prolongation of time, the MW of PLA decreased remarkably. The MW of PLA prepared by all complexes is not very high, which might be related to the crystalline water of complexes. X‐ray study indicated that PLA produced by Ni(II) complex is an amorphous polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3312–3315, 2002     

Elution Behavior of Metal Ions with Mixed Glycine-Nitric Acid Eluents in Dowex 50W-X8 Column: Separation of Th(IV), Ce(IV), Bi(III), Fe(III), and Al(III)

Abstract

Distribution coefficients (K) determined by the batch technique in acidic glycine media using Dowex 50W-X8 cation exchanger (H⁺?form, 100–200 mesh size) revealed that this medium can effectively be employed to separate a number of tetravalent and trivalent metal ions from bivalent metal ions. In fixed glycine (0.40 M) and varying concentration of nitric acid (0.10 to 1.0 M), a number of mixtures containing two or three metal ions were resolved on columns using about 8 g of exchanger. In 0.40 M glycine-1.0 M HNO₃ medium, Th(IV)/Ce(IV) were separated from Al(III)/Fe(III)/Bi(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I) and also Al(III)/Bi(III) from a number of divalent metal ions. In 0.40 M glycine-0.50 M HNO₃ medium, the resolution of following ternary mixtures were also achieved: Th(IV)/Ce(IV)-Al(III)/Bi(III)-Fe(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I). Th(IV)/Al(III)/Fe(III)/Bi(III) were also separated from other divalent metal ions in 1.60 M glycine-0.50 M HNO₃ medium. The values of K, elution characteristics of metal ions, elution curves, and the results of the resolution of a number of mixtures of metal ions along with standard deviations are reported.     

Electrophoretic studies of mixed ligand complexes in solution—copper(II), nickel(II), cobalt(II), uranyl(II) and thorium(IV)—tartarate—nitrilotriacetate

Paper electrophoresis has been used for the study of the equilibria in mixed ligand complex systems in solution. The method is based on the migration of a spot of a metal ion, with the complexants added in the background electrolyte (0.1 M perchloric acid), at a fixed pH. The concentration of one of the complexants [A] is kept constant, while that of second ligand [L] is varied. A graph of—log [L] against mobility is used to obtain information on the formation of the mixed ligand complex, and to calculate the stability constant. Using this technique, the values of overall stability constant of the complex metal—tartarate—nitrilotriacetate have been found to be 10^12.25, 10^5.98, 10^?3.56, and 10^3.74 for Cu(II), Ni(II), Co(II), UO₂(II) and Th(IV) complexes, respectively at μ = 0.1 and temp. = 40°C.     

Host (nanocavity of zeolite-Y)/guest (Mn(II), Co(II), Ni(II) and Cu(II) complexes of pentadendate Schiff-base ligand) nanocomposite materials (HGNM): application in the heterogeneous oxidation of cyclohexene

Transition metal (M = Mn(II), Co(II), Ni(II) and Cu(II)) complexes with pentadendate Schiff-base ligand; N,N′-bis(salicylidene)-2,6-pyridinediaminato, H₂ [sal-2,6-py]; was entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of bis(salicylaldiminato)metal(II); [M(sal)₂]-NaY; in the supercages of the zeolite, and (ii) in situ Schiff condensation of the metal(II) precursor complex with the corresponding 2,6-pyridinediamine; [M(sal-2,6-py)]-NaY. The new materials were characterised by several techniques: chemical analysis, spectroscopic methods (DRS, BET, FTIR and UV/Vis), conductometric and magnetic measurements. Analysis of the data indicates that the M(II) complexes are encapsulated in the nanodimensional pores of zeolite-Y and exhibit different from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix. The Host–Guest Nanocomposite Materials (HGNM); [M(sal-2,6-py)]-NaY; catalyzes the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). Oxidation of cyclohexene with HGNM gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene. [Mn(sal-2,6-py)]-NaY shows significantly higher catalytic activity than other catalysts.     

AGGREGATION BEHAVIOR OF COBALT(II), NICKEL(II), AND COPPER(II) BIS(2-ETHYLHEXYL) PHOSPHATE COMPLEXES IN n-HEPTANE

ABSTRACT

The solution behavior of divalent transition metal-bis(2-ethylhexyl) phosphate (M(DEHP)₂, M = cobalt, nickel or copper) complexes in n-heptane have been investigated by vapor pressure osmometry, viscometry and dynamic light scattering. Co(DEHP)₂ complexes tend to form large macromolecular species with a mean aggregation number N_agg as large as 225, and the size of the macromolecular species decreases with increasing Co(DEHP)₂ concentration. In contrast, Cu(DEHP)₂ complexes tend to form small macromolecular species N_agg = 4-8 which increase in size with increasing Cu(DEHP)₂ concentration. On the other hand, Ni(DEHP)₂ complexes (and Ni(DEHP)₂-2H₂O complexes when the molar ratio of H₂O     

1,5-Bis(2,5-Difluorophenyl)-3-Mercaptoformazan. A New Tetrafluorinated Dithizone Analogue

Abstract

1,5-Bis(2,5-difluorophenyl)-3-mercaptoformazan (2,2′, 5.5′-tetrafluorodithizone, F₄ H₄ Dz) has been synthesized; its electronic spectra was found to be significantly different from that of dithizone. Its pH_½ in chloroform (8.4) and in carbon tetra-chloride (7.4) are lower than the corresponding values (10.6 and 8.8, respectively) for dithizone. The partition coefficient of the reagent is remarkably decreased in chloroform (270) and in carbon tetrachloride (160) due to the presence of fluorine atoms, compared to the corresponding values (10⁴.89 and 10⁴.18, respectively) for dithizone. The extraction constants of its complexes with Cd(II), Cu(II), Pb(II), Co(II), Hg(II), and Zn(II) were found to be higher than the corresponding values of dithizone complexes, thus enabling their extraction from more acidic solutions. The new reagent seems also to be slightly more sensitive for Bi(III), Cd(II), Co(II), Cu(II), and Hg(II).     

Search for Optimum Conditions of Extraction of Transition Metal Complexes with Alkylimidazoles. I. Extraction of the Co(II), Ni(II), and Zn(II) Complexes of 1-Methylimidazole and of the Co(II) and Zn(II) Complexes of 2-Methylimidazole

Abstract

It has been shown that for the Co(II), Zn(II), and Ni(II) complexes of 1-methylimidazole and for the Co(II) and Zn(II) complexes of 2-methylimidazole, the partition coefficient D between the aqueous and organic phases is proportional to the degree of formation α _n of a definite complex. Tetrahedral species have been found to be extracted with the Co(II) and Zn(II) complexes of 2-methylimidazole and with the Zn(II) complexes of 1-methylimidazole.     

Antibacterial Co(II), Cu(II), Ni(II) and Zn(II) Complexes of Thiadiazoles Schiff Bases

Schiff bases were obtained by condensation of 2-amino-l,3,4-thiadiazole with 5-substituted-salicylaldehydes which were further used to obtain complexes of the type [M(L)(2)]Cl(2), where M=Co(II), Cu(II), Ni(II) or Zn(II). The new compounds described here have been characterized by physical, spectral and analytical data, and have been screened for antibacterial activity against several bacterial strains such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. The antibacterial potency of these Schiff bases increased upon chelation/complexation, against the tested bacterial species, opening new aproaches in the fight against antibiotic resistant strains.     

Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2)

Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.     

Synthesis, Characterization and Biological Properties of Tridentate NNO, NNS and NNN Donor Thiazole-Derived Furanyl, Thiophenyl and Pyrrolyl Schiff Bases and Their Co(II), Cu(II), Ni(II) and Zn(II) Metal Chelates

2-Aminothiazole undergoes condensation reactions with furane-, thiophene- and pyrrole-2-carboxylaldehyde to give tridentate NNO, NNS and NNN Schiff bases respectively. These tridentate Schiff bases formed complexes of the type [M (L)(2)]X(2) where [M=Co(II), Cu(II), Ni(II) or Zn(II), L=N-(2-furanylmethylene)-2-aminothiazole (L(1)), N-(2-thiophenylmethylene)-2-aminothiazole (L(2), N-(2-pyrrolylmethylene)-2-aminothiazole (L(3)) and X=Cl. The structures of these Schiff bases and of their complexes have been determined on the basis of their physical, analytical and spectral data. The screening results of these compounds indicated them to possess excellent antibacterial activity against tested pathogenic bacterial organisms e.g., Escherichia coli, Staphylococcus aureous and Pseudomonas aeruginosa. However, in comparison, their metal chelates have been shown to possess more antibacterial activity than the uncomplexed Schiff bases.     

New polymeric Schiff base and its metal complexes

A novel polymeric Schiff base was synthesized by the reaction of a Schiff base from 2,4‐dihydroxy benzaldehyde and aniline with acryloyl chloride and was polymerized in methyl ethyl ketone at 70°C with benzoyl peroxide as a free‐radical initiator. Polychelates were obtained in an alkaline solution of poly(2‐hydroxy‐4‐acryloyloxy‐N‐phenylbenzylidine) with aqueous solutions of metal ions such as Cu(II), Ni(II), Co(II), Ca(II), Cd(II), Mn(II), and Zn(II). The polymeric Schiff base and polychelates were characterized with elemental analysis and spectral studies. The elemental analysis of the polychelates suggested that the metal‐to‐ligand ratio was 1:2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polychelates of the Cu(II) complex were square‐planar, those of the Ni(II), Mn(II), and Co(II) complexes were octahedral, and those of the Ca(II), Cd(II), and Zn(II) complexes were tetrahedral. X‐ray diffraction studies revealed that the polychelates were highly crystalline. The thermal properties of the Schiff base and polychelates were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 494–500, 2004     

Simultaneous determination of trace aluminum (III), copper (II) and cadmium (II) in water samples by square-wave adsorptive cathodic stripping voltammetry in the presence of oxine

A validated adsorptive cathodic stripping voltammetry method is described for simultaneous determination of Al(III), Cu(II) and Cd(II) in water samples. In acetate buffer (pH 5) containing 10 μM oxine, these metal ions were determined as oxine complexes following adsorptive accumulation onto the HMDE at −0.05 V versus Ag/AgCl/KCl_s. The best signal to noise ratio was obtained using a square wave of scan increment 10 mV, frequency 120 Hz, and pulse-amplitude 25 mV. Limits of detection as low as 0.020 μg L⁻¹ Al(III), 0.012 μg L⁻¹ Cu(II) and 0.028 μg L⁻¹ Cd(II) were achieved. Interference due to various cations (K(I), Na(I), Mg(II), Ca(II), Mn(II), Fe(III), Bi(III), Sb(III), Se(IV), Pb(II), Zn(II), Ni(II), Co(II)), anions (Cl⁻, NO³⁻, SO₄ ²⁻, PO₄ ³⁻) and ascorbic acid was minimal as the measured signals change by 4% at the maximum. The stripping voltammetry method was successfully applied for simultaneous determination of Al(III), Cu(II) and Cd(II) in tap and natural bottled water samples.     

Thermal properties of poly(N-maleyl glycine), poly(N-maleyl glycine-co-acrylic acid), and their metal complexes

The thermal properties of two water-soluble polymers; poly(N-maleyl glycine) and poly(N-maleyl glycine-co-acrylic acid) as well as their metal complexes with Co(II), Zn(II), Ni(II), Cu(II), Fe(III), Cd(II), Pb(II), and Hg(II) ions were investigated. The copolymer-metal ion complexes were obtained in aqueous phase by using the Liquid Phase Polymer-Based Retention (LPR) technique in conjunction with membrane filtration. The water-soluble P(MG) and P(MG-co-AA) are shown to be useful for the retention of different metal ions and their separation from elements not bound to the polymeric reagent. The thermal stability of the copolymer-metal ion complexes under nitrogen atmosphere at 20–500°C was also investigated. The complexes with different transition were characterized with FT-IR and thermogravimetry (TGA). From the TGA data the thermal decomposition temperature (TDT) and kinetic parameters such as activation energy (Ea) and reaction order (n) were determined. Received: 21 April 1998/Revised version: 16 July 1998/Accepted: 22 July 1998     

A mononuclear copper(II) complex of a protonated unsymmetrical dinucleating Schiff base ligand

Reaction of the unsymmetrical and potentially dinucleating Schiff base ligand HL¹ with copper(II) salts has given mono- and dinuclear metal complexes. The structure of a mononuclear complex of diprotonated HL¹, [Cu(H₂L¹)(OH₂)](ClO₄)₃·H₂O·CH₃OH_, has been determined.     

Mechanism of cytotoxicity and cellular uptake of lipophilic inert dinuclear polypyridylruthenium(II) complexes

The accumulation, uptake mechanism, cytotoxicity, cellular localisation of—and mode of cell death induced by—dinuclear ruthenium(II) complexes ΔΔ/ΛΛ‐[{Ru(phen)₂}₂{μ‐bb_n}]⁴⁺ (Rubb_n), where phen is 1,10‐phenanthroline, bb_n is bis[4(4′‐methyl‐2,2′‐bipyridyl)]‐1,n‐alkane (n=2, 5, 7, 10, 12 or 16), and the corresponding mononuclear complexes containing the bb_n ligands, were studied in L1210 murine leukaemia cells. Cytotoxicity increased with linker chain length, and the ΔΔ‐Rubb₁₆ complex displayed the highest cytotoxicity of the series, with an IC₅₀ value of 5 μM , similar to that of carboplatin in the L1210 murine leukaemia cell line. Confocal microscopy and flow cytometry studies indicated that the complexes accumulate in the mitochondria of L1210 cells, with the magnitude of cellular uptake and accumulation increasing with linking chain length in the bb_n bridge of the metal complex. ΔΔ‐Rubb₁₆ entered the L1210 cells by passive diffusion (with a minor contribution from protein‐mediated active transport), inducing cell death via apoptosis. Additionally, metal‐complex uptake in leukaemia cells was approximately 16‐times that observed in healthy B cells highlighting that the bb_n series of complexes may have potential as selective anticancer drugs.     

Synthesis and spectroscopic characterization of N-substituted thiosemicarbazone complexes

Complexation between Co(II), Ni(II), and Cu(II) with some 3,4-hexanedione bis[N-substituted thiosemicarbazones] has been investigated. The ligands release the two hydrazine hydrogens during the complex formation and act as binegative tetradentate (N₂S₂) except [Cu(H₂Hx4M)Cl₂] and [Cu(H₂Hx4Et)Cl₂]2H₂O in which the ligands behave as neutral tetradentate. The magnetic moments and electronic spectra provide information about the geometry of the complexes, which is supported by calculating the ligand field parameters for the Co(II) complexes. Most Ni(II) complexes are diamagnetic, indicative of a square-planar structure. The bands observed in Nujol are shifted to higher energies in dimethylformamide (DMF) solution, suggesting a weak interaction with the solvent. The ESR spectra of the complexes in solid and DMF solution exhibit axial symmetric g-tensor parameters with g _|>g _⊥>2.0023. The molecular parameters of [Ni(Hx4M)] have been calculated theoretically by semiempirical PM3 method. Also, the electronic transitions were calculated theoretically and found approximately similar to those recorded experimentally.     

Synthesis,spectral and structural study of sulfur-containing copper(II) complexes

A series of four new copper(II) complexes [Cu(H₂L)(L¹)] 1, [Cu(H₂L)(PMDT)] 2, [Cu(H₂L)(Dien)] 3 and [Cu(H₂L)(L²)] 4 have been synthesized by template condensation (H₂L=thiodiglycolic acid, L¹=N-[(1)-1-(4-methylphenyl)ethylidene]benzohydrazide, PMDT=N,N,N′,N′,N ^′′-pentamethyldiethylene- triamine, Dien=diethylenetriamine L²=N-[(1)-pyridin-2-ylmethylidene]benzohydrazide). The bonding and stereochemistry of the complexes have been characterized by molar conductance, elemental analysis, magnetic susceptibility, infrared, UV–visible, electron paramagnetic resonance structural studies and electrochemical studies. g-Values were calculated for all complexes in polycrystalline form as well as in DMSO solution. The magnetic and spectral data indicate square pyramidal geometry for 1 and octahedral geometry for 2–4 complexes. Cyclic voltammograms for all the complexes are similar and involve two irreversible redox processes. Their biological properties have also been studied. The thio complexes show more antibacterial activity than the controlled one. The antibacterial activities of the compounds have also been tested against Escherichia coli with different concentrations.     

Structural diversity in Cu(II) and Cd(II) coordination complexes with 4-amino-1,2,4-triazole ligand

The syntheses and structures of the series of metal complexes, namely [CuCl₂(L)₂·H₂O)]_n (L = 4-amino-1,2,4-triazole), 1; {[Cu(L)₄][ClO₄]₂.H₂O}_n, 2; and [Cd₂Cl₄(L)₂.2H₂O]_n, 3 are reported. These were prepared by the self-assembly of Cu(II) and Cd(II) salts with L in MeOH/H₂O system. All these complexes have been characterized by elemental analysis, IR spectrum, and single crystal X-ray diffraction. Complexes 1–2 show 1-D polymeric infinite chains, while complex 3 shows 2D pleated net. The anions Cl⁻ in complexes 1 and 3 act as bridging or terminal ligands to the metal atoms while the ClO₄⁻ anions in 2 are not coordinated to the metal centers.     

Conductometric studies of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates in N,N—dimethylacetamide solutions

Results are reported for the molar conductivities at 25°C of N,N—dimethylacetamide (DMA) solutions of Bu₄NBF₄ and Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates. The limiting molar conductivities of [M(DMA)₆]²⁺ (M  MN, Co, Ni, Cu, Zn) and BF^?₄, as well as association constants for Co(BF₄)₂ in DMA solutions have been calculated. The slight differences between conductometric curves of different metal ions are discussed.     

THE BEHAVIOUR-STRUCTURE RELATIONS IN THE EXTRACTION OF COBALT(II), NICKEL(II), COPPER(II) AND CALCIUM(II) BY KONOACIDIC ORGANOPHOSPHORUS EXTRACTANTS

The reaction stoichiometrics were studied in the extraction of Co(II), Ni(II), Cu(II) and Ca(II) by n-octyl, 1-methylheptyl and 2-ethylhexyl hydrogen styrylphosphonates and di-2-ethylhexylphosphoric acid and 2-ethylhexyl hydrogen 2-ethylhexylphosphonate. The ultraviolet-visible and infrared spectra were recorded for these extractants and their complexes with the above metals. Based on the experimental data, an empirical relationship was established between the structure of the extractants and the extracting behavior: pH_½ = ApKa + Bν_p=0 - c where pKa and ν_p=0 are the acid dissociation constant of the extractants and the characteristic frequency of infrared absorption for the P=0 group, respectively. The values of A, B and C depend on the extracted metals. The analysis of the relationship between the steric effect of substituting groups and extracting power seems to indicate that the steric effect has been implied in the coefficients A, B and C.