Extraction of copper(II) from ammonium chloride solutions with capric acid

Extraction of copper(II) with capric acid from ammonium chloride solutions was examined. The composition of the complex extracted was determined and it was found that the extraction process can be adequately described by the equation: 2Cu_(a)²⁺ + 3(HR)_2,(0) ⇌ (CuR₂·HR)_2,(0) + 4H_(a)⁺     

Ethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic) acid as complexing agent

Metal derivatives of ethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic) acid (EDTMP, H₈L) with some bivalent ions—Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) have been isolated in various stoichiometric ratios from aqueous medium. Electronic spectra indicate them to be six-coordinated. EPR studies of Cu(II) complexes show that they are tetragonally elongated. Magnetic moments of M₄L derivatives are very low due to antiferromagnetic exchange interactions, but the moments go on increasing for M₃Na₂L and M₂Na₄L and are normal for MNa₆L derivatives, due to isolation of paramagnetic centres by diamagnetic sodium ions. IR spectra and thermal stability of the complexes have also been studied.     

N,N'-双水杨酰代乙二胺合铜(II)酸根和N,N'-1,2-双水杨酰代丙二胺合铜(II)酸根的Cu(II)-Co(II)双核酸合物的合成和磁性

本文合成了两个新型双核配合物, [Cu(Samen)Co(L)2]和[Cu(Sampn)Co(L)2], Samen^4^-表示N,N'-双水杨酰代乙二胺根阴离子,Sampn^4^-表示N,N'-1,2-双水杨酰代丙二胺根阴离子, L表示5-硝基-1,10-菲咯啉(NO2-Phen)。经元素分析, IR和电子光谱等推定配合物具有酚氧桥结构,Cu(II)及Co(II)的配位环境分别为平面四方及畸变八面体构型。测定了配合物(4-300K)的变温磁化率, 并用最小二乘法和自旋Hamiltonian算符,H=2JS1.S2-DSzl导出的磁方程拟合, 求得交换参数为J=-4.39(Samen)和-3.59cm^-^1(Sampn), 表明两个Cu(II)-Co(II)双核配合物中有弱的反铁磁性超交换相互作用。     

N,N'-乙二水杨酰胺合铜(II)酸根和N,N'-1,2-丙二水杨酰胺全铜(II)酸根的双核Cu(II)-Fe(III)配合物的合成和磁性

本文合成了四个新型双核配合物、[Cu(samen)Fe(L)Cl]和[Cu(sampn)Fe(L)Cl]。经元素分析、IR, 电导、磁性测量等手段推定配合物具有酚氧桥结构, Cu(II)及Fe(III)的配位环境分别为平面四方及四角锥的构型, Fe(III)离子的自旋态S=3/2。测定了配合物[Cu(samen)Fe(L)Cl]的变温磁化率(4-300K), 参数J和θ值表明两个双核配合物中金属离子之间有中等程度的反铁磁性超交换作用和双核单元之间有弱的分子间相互作用。     

N,N'-1,2-丙二水杨酰胺合铜(II)酸根的双核Cu(II)-Ni(II)配合物的合成和磁性

本文合成了两个新的双核配合物, [Cu(sampu)Ni(L)2], sampn^4^-表示N,N'-1,2-丙二水杨酰胺阴离子, L表示2,2-联吡啶(bpy)或1,10-菲咯啉(phen),经元素分析, IR和电子光谱等方法已推定配合物具有酚氧桥结构和Cu(II)及Ni(II)的配位环境分别为平面四方及八面体构型, 配合物的变温磁化率已测(4-300K), 其数值用最小二乘法和从自旋哈密顿算符H=-2JS1S2导出的磁方程拟合, 求得交换参数为J=-1.90cm^-^1(pby)和J=1.68cm^-^1(phen), 表明两个Cu(II)-Ni(II)双核配合物中有弱的反铁磁自旋交换相互作用。     

Amino acid and peptide bioconjugates of copper(II) and zinc(II) complexes with a modified N,N-bis(2-picolyl)amine ligand

Four chelating nitrogen ligands 2-5 derived from N,N-bis(2-picolyl)amine (bpa, 1) were synthesized, namely, (PyCH(2))(2)N-CH(2)-p-C(6)H(4)-CO(2)R (R = Me, 2, and R = H, 3) and (PyCH(2))(2)N-(CH(2))(n)-CO(2)H (n = 2, 4, and n = 5, 5). Amino acid conjugates 6 and 7 were formed by condensation of 3 with H-Phe-OMe and H-betaAla-OMe, respectively. Cu(II) and Zn(II) complexes of 1-7 were prepared and fully characterized. The X-ray structures of 1(Zn), 2(Zn), 4(Cu), and 7(Cu) were determined. The Zn complexes 1(Zn) and 2(Zn) as well as 7(Cu) show a distorted trigonal bipyramidal coordination environment in the solid state. An octahedral complex is observed for 4(Cu) which forms chains along the crystallographic b axis by intermolecular coordination of the carboxylic acid to the metal ion of a neighboring complex. Ligand 3 was used to prepare the peptide bioconjugate 8 (3-Ahx-Pro-Lys-Lys-Lys-Arg-Lys-Phe-NH(2)) with a nuclear localization signal (nls) heptapeptide by solid phase synthesis. Cu(II) and Zn(II) complexes of 8 were synthesized in situ and studied by FAB-MS, ESI-MS, UV/vis, and EPR (for 8(Cu)), and FAB-MS, ESI-MS, and NMR (for 8(Zn)). All spectroscopic results clearly support metal coordination to the bpa ligand in the bioconjugates 8(M), even in the presence of other potential ligands from amino acid side chains of the peptide. We suggest metal-peptide conjugates like 8(M) as artificial metallochaperones because they have the potential to deliver metal ions to specific compartments in the cell as determined by the peptide moieties.     

N,N'-双(2-氨基丙基)草酰胺合铜(II)的铜(II)-锰(II)配合物的合成和磁性

合成和表征了两种新的异双核配合物[Cu(oxap)Mn(L)~2](ClO~4)~2, oxap表示N,N'-双(2-氨基丙基)草酰胺根阴离子, L表示1,10-邻菲咯啉(phen)和5-硝基-1,10-邻菲咯啉(NO~2-phen)。测定了配合物的变温磁化率(4.2-300K), 并用最小二乘法和从自旋Hamiltonian算符, ^^H=-2J^^S~1.^^S~2-D^^S~Z~1导出的磁方程拟合。求得交换积分为J=-74.72cm^-^1(phen)和J=-76.39cm^-^1(No~2-phen), 表明两个Cu(II)-Mn(II)双核配合物中有中等强度的反铁磁超交换作用。     

Crystal and molecular structures of bis(N-propionamido-glycinato) copper(II) hydrate,bis(N,N-dipropionamido-glycinato) copper(II) dihydrate and bis(N,N-dipropionamido-glycinato)-μ-carboxylato-dicopper(II) perchlorate hydrate

Summary The three title compounds were prepared and their X-ray crystal stuctures were determined. All three compounds were found to contain extensive hydrogen bonding.     

Extraction of copper(II) and nickel(II) by nopinoquinone dioxime

In the research for a selective extractant for nickel a strained dioxime, β-nopinoquinone dioxime, has been studied in its extraction properties for copper(II) and nickel(II). Spectroscopic investigations (ESR and NMR) showed that both copper and nickel are extracted as a N,N-coordinated chelate. The extraction studies showed that the use of strained instead of aliphatic dioximes makes the extraction more convenient because of the higher extraction rate, but the selectivity for nickel above copper disappears.δ-nopinoquinone dioxime is easily converted into its furazan by treatment with 1N NaOH. This furazan is a rather weak ligand without significant extraction capacities.     

Synthesis,spectroscopy and thermal analysis of nickel(II), palladium(II) and copper(II) complexes with N,N′-bis(2-hydroxyethyl)-oxamide

Summary The new complexes K₂[Ni(H₂heo)₂]·3H₂O, K₂[Pd-(H₂heo)₂], K₂[Cu(heo)]·3H₂O and [Cu₂(heo)·2H₂O] {heo = [(CONCH₂CH₂O)₂]^4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN₄ coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu₂(heo)·2H₂O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H₂O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.     

Synthesis and characterization of copper(II) complexes with 3-methylpicolinic acid. Crystal and molecular structure of bis (3-methylpicolinato- N,O )(4-picoline)copper(II)

Copper(II) complexes of 3-methylpicolinic acid (3-MepicH), namely [Cu(3-Mepic)₂] · 2H₂O (1) and [Cu(3-Mepic)₂(4-pic)] (2) were prepared and characterized by IR spectroscopy and thermal analysis (TGA/DTA). Crystal structure for 2 was determined by X-ray crystal structure analysis. 1 was prepared by reaction of copper(II) sulfate pentahydrate and 3-methylpicolinic acid in aqueous solution, while 2 was prepared by recrystallization of 1 from 4-picoline solution. Structure analysis revealed square-pyramidal copper(II) coordination and N,O-chelating mode of 3-methylpicolinic acid in 2. Copper(II) is coordinated by two 3-Mepic ligands in the basal plane of a square pyramid and by 4-picoline in the apical position. Crystal packing of 2 is dominated by weak intermolecular C–H ··· O hydrogen bonds and π ··· π stacking interactions forming a complex three-dimensional supramolecular architecture.     

Synthesis and magnetic properties of copper (II)-manganese (II) compounds with N,N′-ethylenedisalicylamidatocuprate(II)

By the reaction of sodium N,N′-ethylenedisalicylamidatocuprate ( I ) pentahydrate, Na₂[Cu(samen)]·5H₂O, with a manganese ( I ) salt and 2,2′-dipyridyl (bpy) or 1,10-phenanthroline (phen), the binuclear metal complexes [Cu(samen) Mn(L)₂] (L ? bpy, phen) have been synthesized. Based on IR, elemental analyses and electronic spectra, the complexes are proposed to consist of a four-coordinated Cu( I ) in a distorted planar environment and Mn( I ) in a distorted octahedron. The complexes have been characterized with variable-temperature magnetic susceptibility (4.2—300 K) and the susceptibility data were least-squares fit to susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for Mn²⁺ ion, H?—2JS₁·S₂—DS, where D is the axial zero-field splitting parameter for the Mn(II) ion. The exchange integral, J, was found to be —34.6 and —28.8 cm^?1 for [Cu(samen)Mn(bpy)₂] and [Cu(samen)Mn(phen)₂] respectively. The weak antiferromagnetic spin-exchange interaction can be interpreted by considering σ-π exchange pathway.     

Extraction behaviour of copper(II) and silver(I) with a thiacrown ether carboxylic acid, 2-(3,6,10,13-tetrathiacyclotetradec-1-oxy)hexanoic acid

The extraction behaviour of copper(II) and silver(I) with 2-(3,6,10,13-tetrathiacyclotetradec-1-oxy)hexanoic acid (TTCTOHA) was investigated at 25+/-0.1 degrees C and ionic strength of 0.1. The value of the logarithmic distribution coefficient, logK(DR) of TTCTOHA between octan-1-ol and aqueous phases was determined to be 4.13. Copper(II) was extracted with TTCTOHA into octan-1-ol as CuL(2), where L represents the anionic species of TTCTOHA. The logarithmic extraction constant, logK(ex(10)), was determined at -7.42. Silver(I) was extracted with TTCTOHA into octan-1-ol as AgL and Ag(2)L(2). The logarithmic distribution constant, logK(DC), of AgL was estimated to be 0.49. On the other hand, silver(I) was extracted into 1,2-dichloroethane as AgL and the logarithmic extraction constant, logK(ex(10)), was determined to be -2.24.