Copper Complexes Obtained from the Schiff Base of Quinoline-2-Aldehyde and Aliphatic Diamines

Schiff base bis (2— quinolidene)- diamine gives a purple-red complex with copper ions with a λ_max at 530 mμ. The optimum pH for production of this complex is approximately 9.5. None of the metallic ions of the analytical groups II and III give rise to red complexes with the above Schiff base. Manganous (Mn²⁺) and stannous (Sn²⁺)ions as well as reducing agents such as hydrazine or hydroxylamine exert a catalytic effect on the rate of formation of these copper complexes. The thermal stability of the copper complex formed from the Schiff bases (2-quinoline-aldehyde with NH₂-(CH₂)_n-NH₂) is greater for diamine for which n = 4–6 than for n = 2–3.     

Synthesis and characterization of novel Schiff‐base polyamides from copper/benzil bisthiosemicarbazone complexes

A new copper‐containing Schiff‐base diamine, benzil bis(thiosemicarbazonato)copper(II) (CuLH₄), was synthesized in two steps from benzil bisthiosemicarbazone (LH₆). The ligand LH₆ and the complex CuLH₄ were characterized with Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. CuLH₄ was used to prepare novel polyamides. The low‐temperature solution polycondensation of the complex CuLH₄ with various aromatic and aliphatic diacid chlorides afforded copper‐containing Schiff‐base polyamides with inherent viscosities of 0.25–0.36 dL/g in N,N‐dimethylformamide (DMF) and 0.75 dL/g in H₂SO₄ at 25°C. The polyamides were generally soluble in a wide range of solvents, such as DMF, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, tetrachloroethane, hexamethylene phosphoramide, N‐methylpyrrolidone, and pyridine. Thermal analysis showed that these polyamides were practically amorphous, decomposed above 270°C, and exhibited 50% weight loss at and above 400°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Soluble and insoluble ternary complexes of serum proteins with polyanions in the presence of Cu2+ in water

Complex formation between polyacrylic acid (PAA) and bovine serum albumin (BSA), human serum albumin (HSA), hemoglobin (Hb), globin (Gl), and, respectively, transferrin (Tr), were studied in neutral water. Water-soluble and insoluble complexes are formed upon addition of divalent copper ions to the solution. The contacts between proteins and PAA are achieved via chelate unit formation in which the copper ions are located at the center. The solubility of the polycomplexes depends on the nature of proteins and correlates with their isoelectric points (pI). In the mixtures of Hb–Cu²⁺–PAA and Gl–Cu²⁺–PAA, insoluble complexes are formed at pH = pI starting with very low concentrations of Cu²⁺ (n_cu/n_AA ≤ 0.01). On the other hand, these polycomplexes remain soluble at pH > pI. BSA, HSA, and Tr form soluble ternary polycomplexes at neutral water (pH 7). The formation of the polycomplexes in the mixture BSA&–Cu²⁺–PAA was intensively studied by titration, HPLC, electrophoretic, and spectrophotometric methods. The solubility, composition, and stability of these polycomplexes depend on metal/polymer and protein/polymer ratio. Insoluble polycomplexes are formed when concentration of Cu²⁺ reaches a critical value (n_Cu/n_AA ≥ 0.25). At this concentration of Cu²⁺, phase separation takes place, starting with very low concentration of protein in the system. Over the critical ratio of the protein/polymer, the mixture again exhibits water-soluble character. The pattern of distribution of Cu²⁺ between PAA coils and of protein globules between polymer-metal complex particules appeared to follow the self-assembly principle. A hypothetical structural scheme for the formation of soluble and insoluble ternary polycomplexes is proposed. © 1996 John Wiley & Sons, Inc.     

Microphase separated structure and blood compatibility of segmented poly(urethaneureas) with different diamines in the hard segment

The properties, structures and blood compatibility by platelet adhesion and deformation of segmented poly(urethaneureas) (SPUU's) with various aliphatic diamine chain extenders were investigated. The SPUU's containing diamines with an odd number of methylene units showed a remarkable degree of phase mixing between the hard and soft segments. I.r. spectra of SPUU's indicated that the state of hydrogen bonding depended on the number of methylene units in the diamine. XPS measurements revealed that the surface concentration of soft segment was independent of diamine structure but the state of microphase separation strongly depended on the number of methylene units in the diamine. The SPUU's with an even number of methylene units in the diamines showed less platelet adhesion and deformation than those with an odd number of methylene units in the diamines.     

The Potential Use of Low‐Grade Phosphate Rocks as Adsorbent

This study evaluates the suitability of using low‐grade phosphate for Cu²⁺ removal. The study also investigates the effects of the presence of ethylene‐diamine‐tetra‐acetic acid (EDTA), citric acid, tartaric acid and sodium chloride in a solution containing Cu²⁺ on the adsorption capacity of Cu²⁺ onto low‐grade phosphate. For aqueous solutions with 100 ppm Cu²⁺, the percentage removal of Cu²⁺ at pH 4 onto 0.2 g of 0.063 mm low‐grade phosphate was found to be 96.6 % after one hour. Using one mmol of either Cu²⁺, Cu‐NaCl, Cu‐tartaric acid, Cu‐EDTA, or Cu‐citric acid aqueous solutions, the present work shows trend of the percentage removal of Cu²⁺ at equilibrium time: Cu²⁺ > Cu‐NaCl > Cu‐tartaric acid > Cu‐EDTA > Cu‐citric acid. It is also found that increasing the concentration of ligand to copper ratio decreases the percentage removal of Cu²⁺ significantly. This means that the adsorption capacity is ligand type and concentration dependent.     

Preparation of functionalized ion‐imprinted phenolic polymer for efficient removal of copper ions

In this work, an ion‐imprinted polymeric material based on functionalized phenolic resin was developed for the efficient selective removal of Cu²⁺ ions from aqueous solution. p‐Aminophenol‐isatin Schiff base ligand (HPIS) was first synthesized and combined with Cu²⁺ ions to prepare the corresponding complex [Cu(PIS)₂]. The Schiff base ligand along with its copper complex was fully investigated and characterized before anchoring in a base‐catalyzed condensation copolymerization with formaldehyde and resorcinol. The Cu²⁺ ions were removed from the obtained resin construction and the resulting Cu²⁺ ion‐imprinted material (Cu‐PIS) was employed for the selective extraction of Cu²⁺ ions under different pH values, initial concentrations and contact time conditions. The optimum pH for the removal process was chosen as 6 and the maximum adsorption capacity was 187 ± 1 mg g^–1. Also, the kinetics showed a better fit with the pseudo‐second‐order equations. The selectivity of the prepared Cu‐PIS was also evaluated in a multi‐ionic species containing Ni²⁺, Cd²⁺, Pb²⁺, Co²⁺ besides Cu²⁺ ions and the determined parameters confirmed a superior recognition capability toward the imprinted Cu²⁺ ions. © 2019 Society of Chemical Industry     

Novel building blocks for oligonuclear copper complexes derived from β‐ketoenamines of histidine

Condensation products of L‐histidine with the 3‐oxoenolethers diethyl‐ethoxymethylene‐malonate ( 1 ) and ethyl‐ethoxymethylene‐cyanoacetate ( 2 ) react with copper(II) as di‐anionic ligands to give neutral 1:1 complexes Cu‐ His1 and Cu‐ His2 . Both complexes crystallize as oligonuclear units, even from strongly donating solvents like N‐methylimidazole (Meim) (Cu‐ His1 ) and pyridine (Cu‐ His2 ). X‐ray structure analyses show supramolecular structures, formed of two (Cu‐ His1 ) or four (Cu‐ His2 ) formula units of the complex, which arrange to macrocycles by means of intermolecular coordination of the imidazole‐N. Strong H‐bridges result in a face‐to‐face orientation of the hydrophilic sites of two great rings. ESI‐MS investigations in pyridine solution give evidence for the existence of dimeric, tetrameric and – in case of Cu‐ His2 – trimeric units, besides the monomeric adducts with one pyridine. In contrast to the dimeric or tetrameric (“cubane‐like”) copper(II) complexes of amino alcohols and their β‐ketoenamines, the complexes Cu‐ His1 and Cu‐ His2 show no significant spin coupling from room temperature down to 4 K. The complexes Cu‐ His1 and Cu‐ His2 give no electrochemically reversible Cu^II/I reduction in pyridine. However, the isolation of a stable diamagnetic copper(I) complex of the methylester derivative, Cu^I‐ HisMe1 , supports the assumption, that similar histidine‐derived copper complexes should display reversible redox behaviour and catalytic activity in reactions with O₂.     

Preparation of aminoalkyl celluloses and their adsorption and desorption of heavy metal ions

Aminoalkyl celluloses (AmACs) were prepared from 6-chlorodeoxycellulose and aliphatic diamines H₂N(CH₂)_mNH₂ (m = 2, 4, 6, 8). Their adsorption and desorption of divalent heavy metal ions such as Cu²⁺, Mn²⁺, Co²⁺, Ni²⁺ and their mixtures were also investigated in detail. Adsorption of metal ions on AmACs was remarkably affected by the pH of the solution, the metal ion and its initial concentration, and also the number of methylene units in the diamines. No adsorption of metal ions occurred on AmACs in strongly acidic solutions. However, metal ions were adsorbed rapidly on AmACs from weakly acidic solutions and the amount of adsorption increased with increasing pH. The effectiveness of AmACs as adsorbents decreased with increasing length of the methylene moiety, and AmACs from ethylenediamine (m = 2) was most effective. The adsorption of metal ions on AmACs was in the order Cu²⁺ > Ni²⁺ > Co²⁺ > Mn²⁺. Accordingly, their behavior followed the Irving-Williams series and Cu²⁺ ions were preferentially adsorbed from solutions containing metal ion mixtures. The adsorbed ions were easily desorbed from the AmACs by stirring in 0.1 M HCl.     

The Copper (II) Complexes of Phenyl-2 Pyridyl Ketone and the Triple Complexes Obtained by Adding Ethylenediamine

Copper salts of low pH (1.8–2.5) combine with phenyl-2-pyridyl ketone to form a ketone complex [(Py–CO–C₆H₅)₂Cu]²⁺. An electrically uncharged complex is obtained at pH > 9 [(Py–C(OH)(C₆H₅)O^?)₂Cu]⁰, liberating two protons from two molecules of the ligand. The stability constant of this complex is β = 16.05. By mixing the copper salts (except the halide) containing this ligand with ethylenediamine, a charged triple complex is obtained at pH < 7 [Py–C(OH)(C₆H₅) O–Cu–NH₂C₂H₄NH₃⁺]²⁺. At pH > 9.5, an uncharged triple complex is obtained: {[(Py–C(OH)(C₆H₅)O^?)₂Cu}₂ · NH₂C₂H₄NH₂}⁰. The copper halide salts produce only an uncharged triple complex; the halide ions are coordinated with the copper atoms. All of these complexes in their solid state, are bi- or polynuclear. As a result, they are magnetically subnormal.     

Influence of chemical structure of isophthaloyl dichloride and aliphatic,cycloaliphatic, and aromatic diamine compound polyamides on their chlorine resistance

The influence of the chemical structures of the polyamides on chlorine resistance was studied by measuring their chlorine uptake rates. They were prepared from isophthaloyl dichloride and aliphatic, cycloaliphatic, or aromatic diamines by the solution or interfacial polycondensation method. This study showed that the chlorine resistance was dependent on the chemical structures of the diamine compounds used in the synthesis of the polyamides. We concluded that the polyamides comprising the diamine components with the following chemical structures had higher chlorine resistance: aliphatic or cycloaliphatic diamine compounds with a secondary amino group, aliphatic or cycloaliphatic diamine compounds with a shorter methylene chain length between end amino groups, and aromatic diamine compounds with methyl or chlorine substituents at the ortho position of the amino groups. Chlorine resistance is related to the basicity of the aliphatic and aromatic diamines used. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 201–207, 2000     

Synthesis and Characterization of processable heat resistant poly (amide-imides) for high temperature applications

Summary A series of new polyamide-imides with high thermal stability were synthesized by direct polycondensation of imide containing diamines with various aromatic diacids using polar aprotic solvents. In this technique triphenylphosphite (TPP) and pyridine were used as condensing agents to form polyamide-imide through N-phosphonium salts of pyridine. The various imide containing diamines were prepared by reacting dianhydride (PMDA, BPTDA) with aromatic diamines such as phenylene diamine, 3,3’-dichloro 4,4’-diaminodiphenylmethane and 2,6-diaminopyridine in 1:2 ratio. The diacids containing flexible ether units were prepared by treating diol with aromatic acid (2,4-dichlorobenzoic acid). The polyamide-imides obtained by this technique were characterized by elemental analysis, FTIR and ¹H-NMR. The solubility of these polyamide-imides was found to be good in polar aprotic solvents such as NMP, DMF, and DMAc etc. The viscosity of the polyamide-imides were determined and found to be in the range of 1.21 to 1.76 dl/g indicating the formation of high molecular weight polymers. The thermal stability of the polymers was tested using DSC and the Tg values are in the range of 207–234 °C showing the high thermal stability of the prepared polymers.     

Low cost adsorbents obtained from ash for copper removal

We investigated the utilization of ash and modified ash as a low-cost adsorbent to remove copper ions from aqueous solutions such as wastewater. Batch experiments were conducted to determine the factors affecting adsorption of copper. The influence of pH, adsorbent dose, initial Cu²⁺ concentration, type of adsorbent and contact time on the adsorption capacity of Cu²⁺ from aqueous solution by the batch adsorption technique using ash and modified ash as a low-cost adsorbent were investigated. The optimum pH required for maximum adsorption was found to be 5. The results from the sorption process showed that the maximum adsorption rate was obtained at 300 mg/L when a different dosage of fly ash was added into the solution, and it can be concluded that decreasing the initial concentration of copper ion is beneficial to the adsorption capacity of the adsorbent. With the increase of pH value, the removal rate increased. When the pH was 5, the removal rate reached the maximum of over 99%. When initial copper content was 300 mg/L and the pH value was 5, the adsorption capacity of the zeolite Z 4 sample reached 27.904 mg/g. The main removal mechanisms were assumed to be the adsorption at the surface of the fly ash together with the precipitation from the solution. The adsorption equilibrium was achieved at pH 5 between 1 and 4 hours in function of type of adsorbent. A dose of 1: 25 g/mL of adsorbent was sufficient for the optimum removal of copper ions. For all synthesized adsorbents the predominant mechanism can be described by pseudo-second order kinetics.     

The electrochemical behaviour of copper in alkaline solutions containing sodium sulphide

The electrochemical behaviour of copper in NaHCO₃ solution (pH 9) and NaOH solutions (pH 14) in the presence of sodium sulphide (10^–3 to 5×10^–2m) was investigated by using rotating disc electrode and rotating ring-disc techniques, triangular potential scanning voltammetry and potentiostatic steps. When the potential increases from –1.2V upwards, copper sulphide layers are firstly formed at potentials close to the equilibrium potentials of the Cu/Cu₂S and Cu/CuS reversible electrodes. When the potential exceeds 0.0 V (NHE), the copper oxide layer is electroformed. Pitting corrosion of copper is observed at potentials greater than –0.3 V. The charateristics of copper pitting are also determined through SEM optical microscopy and EDAX analysis. There are two main effects in the presence of sodium sulphide, namely, the delay in the cuprous oxide formation by the presence of the previously formed copper sulphide layer and the remarkable increase of copper electrodissolution when the potential exceeds the cuprous oxide electroformation threshold potential. These results are interpreted on the basis of a complex structured anodic sulphide layer and on a weakening of the metal-metal bond by the presence of adsorbed sulphur on the copper surface.     

PART 3. THE EXTRACTION OF Co2+, Ni2+, Cu2+ AND Zn2+ USING NOVEL DITERTIARY-AMINEEXTRACTANTS

The syntheses of N-N-octyl-2-2'-pyridylimidazole and N,N'-di-n-octyl-(a)-aminopicoline are presented. Their extraction properties are compared with that of an aliphatic diamine N,N,N',N'-tetraoctylethylene-diamine. The reagents, dissolved in chloroform, were used to extract divalent cobalt, nickel, copper and zinc from aqueous chloride medium. Two extraction mechanisms are postulated for the extraction of these metals, and extraction data are discussed in terms of these postulates.

Extraction of the copper(II) ion at low pH values with amines is best effected by the inclusion of aromatic nitrogen atoms into a diamine extractant.     

Anionische Polyamidharnstoffurethan-Ionomere

Dispersions of anionic segmented polyamide urea urethane ionomers were prepared by reaction of NCO-prepolymers with diamines in the presence of tetracarbonic acid dianhydrides. Analysis of the NCO groups indicates that the adduct of two molecules of diamine and one molecule of dianhydride is the in situ formed chain extender. During preparation and storage of the dispersion excess NCO groups react with water under chain extension, whereas a reaction with urea or urethane groups occurs in the absence of a solvent or dispersing agent. The moduli increase with increasing concentration of COO^- groups. Physical crosslinks formed by hydrogen bonding or Coulomb forces can largely be removed by swelling with water.     

Syntheses and structures of a phenoxo-bridged copper(II) distorted cubane and related complexes with 2-hydroxy-N-(2-pyridylalkyl)benzamide ligands

Two new pyridylalkylamide ligands containing phenol groups appended to the amide, 2-hydroxy-N-(2-pyridylmethyl)benzamide (HL^PhOH) and 2-hydroxy-N-(2-pyridylethyl)benzamide (HL^PhOH′), were synthesized. Copper(II) complexes of these ligands were synthesized and characterized by X-ray crystallography, ESI-MS, FTIR, UV/Vis, and EPR spectroscopy. When basic Et₃N was used to deprotonate the ligands, tetracopper(II) [Cu₄(L^PhO)₄] (1) or dicopper(II) [Cu₂(L^PhO′)₂(CH₃OH)₂] (3) were formed. When base was not used, mononuclear [Cu(HL^PhOH)₂Cl₂] (2) resulted. Complex 1 possesses a distorted cubane-like structure, with the ligands bridging via the phenoxo oxygen atoms, and the copper atoms possessing a distorted square planar geometry. The ligands in dimeric complex 3 also bridge between copper(II) atoms via the phenoxo oxygen atoms, and the copper atoms are square pyramidal. Monomeric 2 is a tetragonally distorted six-coordinate species with pyridyl N atoms and chloride ligands in the equatorial plane, and long interactions with the amide carbonyl O atoms in the axial positions.     

一种不对称希夫碱配合物的合成及其对氯仿分子的选择性识别

利用邻苯二胺的分步缩合反应得到不对称希夫碱（HL）并合成了相应的金属配合物.采用自制空气舱进行氯仿清除率测量,配体HL和配合物MgL、CaL、TiL、Cr （Ⅲ）L、Co（Ⅱ）L、NiL、CuL、ZnL等对氯仿清除率的测量结果对比表明,铜配合物CuL对氯仿具有显著的清除效果.对铜配合物CuL和氯仿形成的单晶进行了晶体结构分析,发现氯仿分子已稳定地包合于配合物晶体骨絮中,并且氯仿分子上的氢和配体上的2个氧原子形成了氢键,其距离分别为2.176和2.637 A,这是由于氯仿分子中氢原子具有一定的酸性以及Cu（Ⅱ）的外围3d9电子构型中的单电子对该氢键的形成也起到一定的促进作用.     

Practical Enantioselective Synthesis of β‐Lactones Catalyzed by Aluminum Bissulfonamide Complexes

The development of an efficient and practical aluminum‐bissulfonamide complex catalyzed enantioselective formation of β‐lactones by [2+2] cycloaddition of ketene (generated in situ from acetyl bromide by dehydrobromination) with various α‐unbranched and ‐branched aliphatic aldehydes is presented. The methodology offers the advantage of operational simplicity not only as the ligand synthesis requires just a single sulfonylation step from commercially available enantiomerically pure diamines. The products are formed in high to excellent yields with ee values typically ranging from 78 to 90 % using 10 mol % of the bissulfonamide ligand. The key finding of this work was a remarkable rate acceleration by using an aluminum/ligand ratio of 1.5:1.     

Soluble Copper Xanthate Complexes

Abstract

When solutions of cupric perchlorate (10^?6 to 10^?2 M) are mixed with solutions containing nonequivalent quantities (concentrations) of xanthate (O-alkyl-dithiocarbonate) ions, clear solutions containing soluble nonionic and ionic complexes are obtained, despite the fact that the solubility product for a given metal xanthate salt may be exceeded by several orders of magnitude. Ultraviolet and visible (UV and VIS) spectroscopy, and dc and ac differential polarography have been employed to study these complex species.

The spectral changes taking place on the addition of potassium ethyl xanthate to cupric perchlorate solutions, and also turbidity measurements, indicate that copper xanthate complexes are formed before the precipitation of cuprous ethyl xanthate, Cu(S₂ COC ₂ H ₅). In very dilute solutions containing near equivalent concentrations of the reactants, a spectrum containing three broad maxima (235, 285, and 375 nm) is obtained and is interpreted as due to a nonionic cupric complex, Cu(S₂ COC ₂ H ₅)₂, (I). In the presence of excess cupric ions a second complex, an ionized cupric monoxanthate, Cu(S₂COC₂H₅)+, (II), is formed with bands at 256, 283, 325, and 382 nm. The relative concentrations of the reactants determine not only which complex is formed in these dilute solutions, but also whether or not the cuprous xanthate precipitates.

The species in solutions giving the spectrum of complex (I) is not stable. It decomposes quickly to cuprous xanthate and dixanthogen. Solutions of the ionic cupric complex (II) are stable for many for many hours. It is suggested that the ionic complex (II) may play a role in activating sphalerite in alkaline solutions.     

Unconventional ion exchange resins and their retention properties for Hg2+ ions

Synthesis of two unconventional ion exchange resins and their behaviour on the mercury sorption experiments were investigated.The ion exchange resins were obtained by the quaternization reaction of 4-vinylpyridine:divinylbenzene copolymer, gel-type, by two ways namely, the nucleophilic substitution of the pyridine matrix with 2-chloroacetamide and the nucleophilic addition of protonated copolymer to acrylamide.Comparative sorptions of Hg²⁺ ions on the synthesized pyridine resins by batch experiments in mono- and binary system were analyzed. Mercury retention experiments aimed to study the influence of the solution concentration, contact time and solution pH. The removal of Hg²⁺ ions from aqueous solutions depends on the pH values, the amount of the retained mercury increased with the pH value.The studied strong base pyridine anion exchange resins presented a good selectivity for the Hg²⁺ ions during the competitive sorption of Hg²⁺/Cu²⁺, Hg²⁺/Zn²⁺ and Hg²⁺/Fe³⁺ at metal cations ratio of 1:1.