Copper Chloride Complexes Research Articles

Polymeric chain complexes of copper(II) chloride with 1,5-disubstituted tetrazoles: Structure and magnetic properties

The complex [Cu(5-(N,N-dimethylaminomethyl)-1-(pyridin-2-yl)tetrazole)Cl2]n (1) was prepared by the reaction of 5-(N,N-dimethylaminomethyl)-1-(pyridin-2-yl)tetrazole with copper(II) chloride in solution. According to the single crystal X-ray analysis, complex 1 presents a 1D coordination polymer, formed at the expense of single chlorido bridges between neighboring pentacoordinated copper(II) cations. The tetrazole acts as a chelating ligand, coordinated via the heteroring N4 atoms and the nitrogen atom of the amino group. The temperature-dependent magnetic susceptibility measurements of complex 1, as well as previously described chain coordination polymers [Cu(1-methyl-5-vinyltetrazole)Cl2]n (2) and [Cu2(1-methyl-5-methylsulfonyltetrazole)2(H2O)2Cl4]n (3), revealed that the copper(II) ions are antiferromagnetically coupled in all the complexes. A superexchange pathway between the metal cations in complex 2 is provided at the expense of double chlorido bridges and the tetrazole ring N3,N4-bridges. In complex 3, this pathway is provided by double chlorido bridges which link alternating Cu(1-methyl-5-methylsulfonyltetrazole)2 and Cu(H2O)2 fragments.

Synthesis, characterization, antifungal and antibacterial activities evaluation of copper (II), zinc (II) and cadmium (II) chloride and bromide complexes with new (E)‐1‐(3,4‐dimethoxybenzylidene)‐4‐methylthiosemicarbazone ligand

The reactions of Cu (II), Zn (II) and Cd (II) chloride or bromide with (E)‐1‐(3,4‐dimethoxybenzylidene)‐4‐methylthiosemicarbazone (MTSVT) lead to the formation of new complexes. They were characterized by spectroscopic studies: IR, 1H and 13C NMR. The crystal structures of the compounds [MTSVT] (L), [ZnBr2(MTSVT)2] (2), [CdCl2(MTSVT)2] (3) and [CdBr2(MTSVT)2.H2O] (4) were determined by X‐ray diffraction. For complexes 2–4, the ion is coordinated through the sulfur atom. All compounds were tested for their antifungal activity against human pathogenic fungi Candida albicans and Aspergillus fumigatus, and for their antibacterial activity against Gram (+) Bacillus subtilis and Enterococcus faecalis as well as against Gram (−) bacteria such as Paracoccus yeei and Acinetobacter baumanii. The results indicated that the metal complexes exhibited a marked enhancement in antibacterial activity compared with the parent Schiff base.

Formation of a nona-nuclear copper(II) cluster with 3,5-di-methyl-pyrazolate starting from an NHC complex of copper(I) chloride.

The complete nona-nuclear cluster in bis-[1,3-bis-(2,6-di-methyl-phen-yl)imid-azol-ium] di-μ-chlorido-tetra-chlorido-octa-kis-(μ-3,5-di-methyl-pyrazolato)hexa-μ3-hydroxido-nona-copper(II) chloro-form disolvate, [HIXy]2[Cu9(μ-pz*)8(μ3-OH)6(μ2-Cl)2Cl4]·2CHCl3 or (C19H21N2)2[Cu9(C5H7N2)8Cl6(OH)6]·2CHCl3, where pz* is the 3,5-di-methyl-pyrazolyl anion, C5H7N2 -, and HIXy is the 1,3-bis-(2,6-di-methyl-phen-yl)imidazolium cation, C19H21N2 +, is generated by a crystallographic centre of symmetry with a square-planar CuII ion bound to four μ3-OH ions lying on the inversion centre. Of the four remaining unique CuII atoms, three adopt CuN2O2Cl square-pyramidal coordination geometries with the chloride ion in the apical position and one has a distorted CuN2OCl tetra-hedral geometry. The dianionic nona-nuclear core can be described as a 24-membered [CuNN]8 ring that contains a Cu9O6Cl6 core. The cluster features three intra-molecular O-H⋯Cl hydrogen bonds. In the crystal, weak C-H⋯N and C-H⋯Cl inter-actions link the components. Polynuclear paramagnetic clusters of this type are of considerable inter-est due to their relevance to both the bioinorganic and single-mol-ecule magnets research fields.

Halido‐bridged Copper(II) Complexes with 1‐tert‐Butyl‐1H‐tetrazole: Crystal Structure and Magnetic Properties

Complex [Cu(tbt)Cl2]n (tbt = 1‐tert‐butyl‐1H‐tetrazole) was prepared by reaction of tbt with copper(II) chloride in solution. According to single‐crystal X‐ray analysis, this complex presents 1D coordination polymer, formed at the expense of double chlorido bridges between neighboring pentacoordinate copper(II) cations. 1‐tert‐Butyl‐1H‐tetrazole acts as monodentate ligand coordinated by CuII cations via the heteroring N4 atoms. The temperature‐dependent magnetic susceptibility measurements of novel complex [Cu(tbt)Cl2]n as well as described previously 1D coordination polymer [Cu(tbt)2Cl2]n, and linear trinuclear complex [Cu3(tbt)6Br6], were carried out. Magnetic studies revealed that the copper(II) ions were weakly ferromagnetically coupled in polymeric copper(II) chloride complexes, whereas complex [Cu3(tbt)6Br6] showed antiferromagnetic coupling.

The effect of chloride ions on copper solvent extraction from sulfate-chloride medium using LIX 984N

The supply of fresh water is becoming an increasingly important issue in hydrometallurgical treatment of mineral ores. The problem may significantly reduce if the extraction process can incorporate the usage of saltwater throughout the whole hydrometallurgical operation. Seawater as the main source of saltwater is a potential alternative to freshwater. In this research, the effect of the chloride ions, in a range of 0 to 40 g/L, on the solvent extraction of copper with LIX 984N was studied. LIX 984N has been commercially used in copper solvent extraction around the world. Increasing the concentration of Cl− was shown to increase the H+ activity and formation of CuCl+ and CuCl2 species. The solution acidity did not have a negative effect on the extent of copper extraction and extraction rate, in the presence and absence of chloride ion, in contrast to recent studies. The chloride addition was even showed to have a positive impact on copper extraction at pHs below 2 and at shorter mixing times. Through thermodynamic studies, it was shown that increasing chloride concentration results in both higher H+ activity and an increase in the activity of copper chloride complexes, of which the latter factor counteracts the former and overall improves the extent of copper extraction. Increasing the chloride concentration was found to negatively affect the copper extraction isotherms. The impact became more significant at lower concentrations of the extractant. It is therefore suggested that cupric chloride complex ion inhibits copper extraction by lowering the extraction driving forces. Also, it was shown that increasing aqueous chloride concentration promotes involvement of more extractant molecules per Cu2+ species in the extraction reaction in contrast to the reaction without chloride ions. The negative effect of chloride ions on copper solvent extraction then is due to the change in the reaction stoichiometry and decrease in the extraction driving force rather than the types of aqueous Cu2+ speciation. The effect of wash stages on the removal of the chloride ion from loaded organic solution was then investigated and the optimum conditions for the wash stage were found at wash solution to loaded organic ratio of 1 to 7 and sulfuric acid concentration of 10 g/L.

Synthesis and Structure of the Copper(II) Chloride Complex with (2-Bromophenyl)thioacetic Acid Morpholide

The cyclization of (2-bromophenyl)thioacetic acid morpholide to 2-(morpholin-4-yl)-1-benzothiophene in the presence of copper(II) chloride has been found to involve intermediate formation of a complex consisting of two thioamide molecules and one copper cation. The complex has been isolated, and its molecular structure parameters have been determined by quantum chemical calculations.

Highly efficient method for oximation of aldehydes in the presence of bis-thiourea complexes of cobalt, nickel, copper and zinc chlorides

Highly efficient method for oximation of aldehydes in the presence of bis-thiourea complexes of cobalt, nickel, copper and zinc chlorides

Synthesis, structural diversity, luminescent properties and antibacterial effects of cadmium(II) and silver(I) coordination compounds with bis(1,2,3-benzotriazol-1-yl)alkanes

A series of bis(benzo-1,2,3-triazolyl)alkanes were prepared by the reaction of 1,2,3-benzotriazole with the corresponding dibromoalkanes. Individual isomers of these flexible polydentate ligands were separated by selective copper(II) chloride complex formation. Seven new coordination compounds of 1,3-bis(benzo-1,2,3-triazol-1-yl)propane (L3), 1,4-bis(benzo-1,2,3-triazol-1-yl)butane (L4) and 1,6-bis(benzo-1,2,3-triazol-1-yl)hexane (L6) with cadmium(II) or silver(I) nitrates were prepared, characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis and luminescence studies. It was found that depending on the solvent used, cadmium(II) nitrate forms discrete binuclear complex with the ligand L3 in acetone and 1D coordination polymer in acetonitrile. Ligands L4 and L6 with longer linkers formed 2D coordination polymers with silver nitrate both in acetone and acetonitrile. Silver coordination polymer with L6 demonstrated bactericidal effect towards Staphylococcus albus, Pseudomonas aeruginosa and Klebsiella pneumonia bacteria.

Superhydrophobic Treatment of Polyurethane Sponge and Its Application in Oil-water Separation

The superhydrophobicity of the polyurethane sponge was realized by attaching the complex of copper and mercaptan on the outer surface of the polyurethane sponge. As a special case, the complex of 1-dodecanthiol and copper chloride was intensively investigated in this study, with emphasis on the influences of concentration, temperature and residence time on the reaction. SEM and EDS were used to analyze the surface structure and elemental composition of the sponge. The superhydrophobicity of the sponge are contributed by the rough treatment on sponge surface. It is found that a large number of long carbon chains appear on the surface reduces the surface energy. The wettability of the surface was determined by a contact angle meter. The material demonstrates great oil-water separation performance and high repeatability in superhydrophobicity during the the separation process of oil and water before first 39 times.

Pyridine-based complexes of copper(II) chloride and bromide: ligand conformation effects on crystal structure. Synthesis, structure and magnetic behavior of Cu(2-Cl-3-X′py)2X2 [X, X′ = Cl, Br

Reaction of copper(II) chloride or bromide with 2-chloro-3-bromopyridine or 2,3-dichloropyridine generates a family of compounds of the general formula L2CuX2 (1–4). X-ray crystallography shows that the bromide complexes (3-bromo-2-chloropyridine)dibromidocopper(II) (1) and (2,3-dichloropyridine)dibromidocopper(II) (3) are particularly unusual in that they crystallize with both the syn- and anti-conformation structures in the same crystal. A review of the literature on complexes of the formula (substituted-pyridine)2CuX2 suggests that these are the first examples of such complexes. The members of the family show a variety of magnetic behaviors and variable temperature magnetic susceptibility data indicate that 1 is essentially paramagnetic (θ = −0.9(1) K) while 3 is weakly ferromagnetic (J = 2.9(1) K). Compound 2 [(3-bromo-2-chloropyridine)dichloridocopper(II)] is fit by the uniform 1-D antiferromagnetic model (J = −19.6(1) K), while 4 [(2,3-dichloropyridine)dichloridocopper(II)] exhibits weak anti-ferromagnetic interactions (J = −3.68(3) K).

Synthesis, structure, and cytotoxicity of complexes of zinc(II), palladium(II), and copper(I) chlorides with (−)-camphor thiosemicarbazone

Complexes [Zn(L2)2Cl2], [Pd2(L2)2Cl4], and CuL2Cl, where L2 is (−)-camphor thiosemicarbazone, were synthesized. The structures of complexes [Zn(L2)2Cl2] and [Pd2(L2)2Cl4] were determined by X-ray diffraction. The crystal structure of complex [Zn(L2)2Cl2] contains mononuclear molecules with distorted tetrahedral {ZnCl2S2} coordination units and monodentate L2 ligands. Complex [Pd2(L2)2Cl4] has binuclear structure with Pd metal centers linked by L2 ligands via μ2-S atoms. Complex CuL2Cl, according to IR and NMR spectra contains S and Cl atoms in the coordination sphere of ion Cu+. Complexes [Pd(tsc)Cl2] and Zn(tsc)2Cl2 (where tsc is thiosemicarbazide) were also obtained to determine the influence of the terpene moiety on cytotoxic properties of these compounds. Mononuclear complex [Pd(tsc)Cl2] contains an NSCl2 planar square coordination polyhedron, and tsc is a bidentate chelate ligand. The effects of tsc, L2, and the complexes with tsc and L2 on viability of the MCF-7 cell line were investigated next. The results showed that tsc and L2 are nontoxic at the tested concentrations (1–50 μM). All the complexes exerted a significant dose-dependent cytotoxic effect, whereas complex CuL2Cl was found to have the lowest half-maximal inhibitory concentration (IC50).

Electrofreezing of the phase-change material CaCl2•6H2O and its impact on supercooling and the nucleation time

This paper reports electrofreezing experiments on the inorganic phase-change material (PCM) CaCl2?6H2O by using an insulated copper electrode that is commonly sold in the market. The effect of the applied voltage or electric field to the nucleation process is measured by the nucleation temperature, freezing temperature, supercooling degree, induction time, time for supercooling, and time for crystallisation. It is found that, compared to the zero field, the freezing temperature remains nearly constant while the nucleation temperature increases with increasing applied field, leading to a reduction in the supercooling degree. The decrease in the supercooling degree is approximately 6 K for an applied voltage of V = 5.0 kV or E = 107 V m-1. With the increase in the applied field the induction time decreased considerably along with reduction of the measured data spread as compared to the no-voltage case, while the crystallisation time for the phase transformation prolonged. The overall phenomena are analysed in terms of modification of the Gibbs free energy for crystallisation owing to the applied field, with the mechanism involving bubble generation and formation of a copper-chloride complex.

2-Chloro-3-fluoropyridine copper(II) complexes and the effect of structural changes on magnetic behavior

A family of copper(II) compounds has been prepared with the general formula (2-chloro-3-fluoro-pyridine)2CuX2·n(Y), where X = Cl, Br, n = 0,1, and Y = methanol or water. For the copper chloride complexes, only solvated structures were obtained (1, X = Cl, Y = H2O; 2, X = Cl, Y = CH3OH) while for the copper bromide compounds, both a desolvated structure and the methanol solvate were prepared (3, X = Br, Y = none; 4, X = Br, Y = CH3OH). Each compound has been characterized by IR, powder X-ray diffraction, single-crystal X-ray diffraction, and temperature-dependent magnetic susceptibility measurement. Compounds 1 and 4 are isostructural, in the space group Cm, and neither exhibits significant magnetic exchange although superexchange pathways are present. Compound 2 also crystallizes in the Cm space group and exhibits weak ferromagnetic interactions (J/kB = 1.72(2) K from the 1D-ferromagnetic chain model) which are likely propagated by hydrogen bonding. Compound 3 crystallizes in the space group P21/n with the Cu(II) ion sitting on a crystallographic inversion center. Compound 3 exhibits weak antiferromagnetic exchange via two-halide superexchange typical for similar complexes. The magnetic data for 3 were fit to the 1D-antiferromagnetic chain model resulting in J/kB = −1.21(1).

NMR Spectra of 1-Vinylimidazole, Transformed by Paramagnetic Complexes

The NMR spectra of 1-vinylimidazole, transformed by the additives of paramagnetic complexes of manganese, cobalt, nickel and copper chlorides with this azole, have been studied. It is shown that the coordination atom in a solution has octahedral surrounding, four ligand molecules being located in the equatorial position. The nature of hyperfine coupling in the above complexes is evaluated by comparison of the experimental constants of hyperfine coupling with theoretically calculated spin densities of unpaired electrons on s-orbitals in the vinylpyrrole radical, which is isostructural to the molecule of 1-vinylimidazole. It is found that in the complexes of cobalt, nickel and copper, the molecules of 1-vinylimidazole are coordinated to the central ion by the pyridine N-3 atom. Therefore, paramagnetic shifts observed for the specified complexes are mainly caused by unpaired spin density delocalized in $$ \sigma $$ - system of the ligand molecule. Notably, in the paramagnetic complex of manganese, hyperfine coupling is transferred both through $$ \sigma $$ - and $$ \pi $$ - systems of the 1-vinylimidazole molecule. Localization of the unpaired spin density is due to the fact that molecules of this azole can also be coordinated by the pyrrole N-1 atom at a certain range of temperatures. In its turn, the specified possibility is explained by non-planar structure of a heterocycle in 1-vinylimidazole.

Crystal structure of the [(1,3-dimesityl-1H-imidazol-3-ium-2-yl)methano-lato]copper(II) chloride dimer: insertion of formaldehyde into a copper-carbene bond.

The crystal structure of bis-[μ-(1,3-dimesityl-1H-imidazol-3-ium-2-yl)methano-lato-κ2O:O]bis-[di-chlorido-copper(II)], [Cu2Cl4(C22H26N2O)2], is reported. The complex is assumed to have formed via the insertion of formaldehyde into the copper-carbon bond in an N-heterocyclic carbene complex of copper(I) chloride. The structure of the binuclear mol-ecule possesses a crystallographic-ally centrosymmetric Cu2O2 central core with the O atoms bridging between the CuII atoms and thus Z' = 0.5. The copper centres are further ligated by two chloride ligands, resulting in the CuII atoms residing in a distorted square-planar environment. The Cu-O bond lengths are shorter than those previously reported in structures with the same central Cu2O2 motif. The complex displays C-H⋯Cl inter-actions involving the H atoms of the heterocycle backbone and the chloride ligands of a neighbouring mol-ecule.

The significance of pH in dictating the relative toxicities of chloride and copper to acidophilic bacteria

The ability of acidophilic bacteria to grow in the presence of elevated concentrations of cationic transition metals, though varying between species, has long been recognized to be far greater than that of most neutrophiles. Conversely, their sensitivity to both inorganic and organic anions, with the notable exception of sulfate, has generally been considered to be far more pronounced. We have compared the tolerance of different species of mineral-oxidizing Acidithiobacillus and Sulfobacillus, and the heterotrophic iron-reducer Acidiphilium cryptum, to copper and chloride when grown on ferrous iron, hydrogen or glucose as electron donors at pH values between 2.0 and 3.0. While tolerance of copper varied greatly between species, these were invariably far greater at pH 2.0 than at pH 3.0, while their tolerance of chloride showed the opposite pattern. The combination of copper and chloride in liquid media appeared to be far more toxic than when these elements were present alone, which was thought to be due to the formation of copper–chloride complexes. The results of this study bring new insights into the understanding of the physiological behaviour of metal-mobilising acidophilic bacteria, and have generic significance for the prospects of bioleaching copper ores and concentrates in saline and brackish waters.

Copper(I) bromide and chloride complexes with urotropine and triethylenediamine: synthesis, crystal structure, and Raman characterization

In the present study, the oxidative dissolution of metallic copper has been explored with the intention to prepare some new complexes with urotropine (hmta) and triethylenediamine (dabco) ligands. All the compounds synthesized were characterized by single-crystal X-ray diffraction and Raman spectroscopy. Reactions performed in a DMSO/CuCl2∙2H2O mixture resulted in [(μ-Cl)2CuI(hdabco+)CuI(μ-Cl)(κS-DMSO)]n and [CuICl(hmta)2] complexes. Their isostructural bromide analogs [(μ-Br)2CuI(hdabco+)CuI(μ-Br)(κS-DMSO)]n and [CuIBr(hmta)2] were prepared by the reaction of elemental copper with respective ligands in a DMSO/CBr4 mixture. Early interrupted reaction of the copper wire with the DMSO/CBr4/dabco solution resulted in an appearance of crystals of the [CuI2Br2(CO)2(dabco)]n carbonyl complex on the copper surface. It arises with the participation of in situ formed carbon monoxide. Despite the identical stoichiometry, the crystal structure of the [Cu2Br2(CO)2(dabco)]n complex is markedly different from that of a known [Cu2Cl2(CO)2(dabco)]n analog.

Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids

A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o‐, m‐, and p‐aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single‐crystal X‐ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (1–4) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 Å) and dimers 2 (3.35 Å) and 3 (3.38 Å). The X‐band polycrystalline EPR spectra of 1–3 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g‐tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin‐triplet EPR spectrum of 5 at 77 K was simulated by using the spin‐Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero‐field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (1–3, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.

Copper(I)–Dioxygen Reactivity in the Isolated Cavity of a Nanoscale Molecular Architecture

Copper(I) and copper(II) complexes supported by a bulky tetradentate N4 ligand, [CuI(TIPT3tren)(CH3CN)]ClO4 (1) and [CuII(TIPT3tren)Cl]BF4 (2), were synthesized and characterized, where TIPT is 2,2′′,6,6′′‐tetraisopropyl‐1,3′:5′,1′′‐terphenyl and tren is tris(2‐aminoethyl)amine. The copper(II) chloride complex 2 exhibits a trigonal‐bipyramidal structure, as usually observed for the tren ligand system, in which the chloride ligand occupies an axial position and is encapsulated in an isolated cavity consisting of three TIPT substituents. Such a trigonal‐bipyramidal structure is stabilized in acetone, in which hydrogen‐bonding interactions between the anilino N–H groups and the oxygen atom of the acetone molecules, entrapped in the hydrophobic clefts between the TIPT substituents, play an important role. The reaction of copper(I) complex 1 and O2 in an acetone‐containing solvent at –110 °C gave end‐on copper(II) superoxide complex 3 together with putative side‐on copper(III) peroxide complex 4, as was evident from detailed studies by variable‐temperature UV/Vis, resonance Raman, and 1H and 2H NMR spectroscopy. The formation of 3 and 4 was also validated by DFT calculations.

Flower-like Cu1.8S nanostructures for high-performance flexible solid-state supercapacitors

In wearable and portable electronic devices, small size, light weight, flexibility, and easy operability are necessary for energy storage systems, such as battery and supercapacitor. To improve the performance, high specific capacity and high energy and power densities are also required. In this study, flower-like Cu1.8S nanostructures are synthesized from a single source tris(thiourea)copper(I) chloride complex precursor. The different-sized Cu1.8S nanostructures with flower-like petal morphology are successfully synthesized by addition of capping agents such as sodium dodecyl sulfate (SDS) and ethylenediaminetetraacetic acid (EDTA) with ethylene glycol (EG) as a solvent. The petal thicknesses vary from 60 to 30 nm, resulting in the increase in its specific surface area. The as-prepared nanostructures are tested for their supercapacitor performances in KOH electrolyte medium. The EDTA-Cu1.8S electrode provides a high specific capacitance of 1050.0 F g−1 as compared with SDS-Cu1.8S (773.0 F g−1) and EG-Cu1.8S (625.4 F g−1). Flexible solid-state symmetric supercapacitors are also fabricated from EDTA-Cu1.8S which deliver a high volumetric capacitance (4.5 F cm−3) and energy density (0.5 mWh cm−3).