Copper Chloride Complexes Research Articles

Synthesis and Characterization of Dichloro bis-thioacetamide Nickel(II) and bis-thioacetamide Copper(II) Chloride Complexes and Formation of Metal Sulphides

Synthesis and Characterization of Dichloro bis-thioacetamide Nickel(II) and bis-thioacetamide Copper(II) Chloride Complexes and Formation of Metal Sulphides

The electronic spectra and the structures of the individual copper(II) chloride and bromide complexes in acetonitrile according to steady-state absorption spectroscopy and DFT/TD-DFT calculations

The results of spectrophotometric study and quantum chemical calculations for copper(II) chloro- and bromocomplexes in acetonitrile are reported. Electronic spectra of the individual copper(II) halide complexes were obtained in a wide spectral range 200–2200 nm. Stability constants of the individual copper(II) halide complexes in acetonitrile were calculated: log β1 = 8.5, log β2 = 15.6, log β3 = 22.5, log β4 = 25.7 for [CuCln]2−n and log β1 = 17.0, log β2 = 24.6, log β3 = 28.1, log β4 = 30.4 for [CuBrn]2−n. Structures of the studied complexes were optimized and electronic spectra were simulated using DFT and TD-DFT methodologies, respectively. According to the calculations, the more is the number of halide ligands the less is coordination number of copper ion.

CATALYSTS OF OXIDATION REACTION OF BUTENE-1 TO METHYLETHYLKETONE

The available and simple metal complex systems of catalytic oxidation of unsaturated hydrocarbons were developed. It is shown that these systems catalyze the selective liquid-phase oxidation of butene-1 to methyl ethyl ketone by molecular oxygen at low temperature. The best results were revealed using Cu(I)Cl monovalent chloride. The catalyst for the production of methylethylketone is a binary system containing complexes of copper and palladium chloride at a molar ratio of 2:1. Hexamethylphosphoramide is used as the ligand and palladium chloride complex as an additional complex contains benzonitrile. A combined catalyst has been offered. It allows to carry out the oxidation reaction of butene to methyl ethyl ketone under mild conditions (low temperature, atmospheric pressure) with high selectivity and yield of the desired product. The proposed binary system is able to coordinate molecular oxygen and butene-1, and thus it becomes possible to conduct the oxidation reaction not directly between butene-1 and O2, and using a specific complex catalyst system allowing them to react with each other in an activated coordinated state. Absorption properties of catalysts synthesized on the bases of transition metals have been studied and activation of molecular oxygen and butane-1 has been determined. As a result of interaction of coordinated oxygen and butane-1 it is possible to carry out oxidation reaction to methylethylketone in mild condition. The specific feature of the offered binary catalyst is irreversible absorption of molecular oxygen. Mild conditions of the reaction proceeding decreases considerably amount of by-products and simplify obtaining and separation of the main product-methylethylketone. Due to the fact that the absorption of O2 is irreversible and it is possible to easily remove the excess amount of O2 after the formation of the oxygen complex. The developed method has the advantage from the point of view of safety.Forcitation:Agaguseynova M.M., Amanullayeva G.I., Bayramova Z.E. Catalysts of oxidation reaction of butene-1 to methylethylketone. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 53-57

Synthesis, Characterization and Biological Activities of Copperchloride (II) Complex Derived From 4 ? Amino Antipyrine, Furfural and DL Cysteine

Synthesis, Characterization and Biological Activities of Copperchloride (II) Complex Derived From 4 ? Amino Antipyrine, Furfural and DL Cysteine

Two synthetic routes to bis(1-methyl-imidazole-2-thione)methane and bis(1-benzyl-imidazole-2-thione)methane complexes including sulfur atom insertion into copper−NHC bonds

The synthesis of novel bis-thione ligand, bis(1-benzyl-imidazole-2-thione)methane, SSBn is reported for the first time. This ligand along with the previously reported bis(1-methyl-imidazole-2-thione)methane, SSMe has been utilised in the synthesis of a series of copper(I) halide complexes. The syntheses have been achieved by two methodologies. The first method involves the direct addition of the ligands to the copper halide salts, CuCl, CuBr and CuI. The second methodology involves an insertion of a sulfur atom into the copper‒NHC bond of the preformed organometallic complexes, [CuBr(CSMe)]2 and [CuI(CSMe)]2 {where CSMe = 1-(3-methyl-2H-imidazol-1-yl-2-thione)methyl-3-methyl-2H-imidazol-2-ylidene} and [CuBr(CSBn)]2 and [CuI(CSBn)]2 {where CSBn = 1-(3-benzyl-2H-imidazol-1-yl-2-thione)methyl-3-benzyl-2H-imidazol-2-ylidene}. These sulfur atom insertion reactions provide an indirect route to the first copper−halide complexes containing the SSMe and SSBn ligands. All six complexes prepared have been fully characterised by spectroscopic and analytical methods as well as X-ray crystallography. Dinuclear structures were obtained for the complexes containing SSMe, mononuclear complexes were obtained for the copper‒chloride and copper‒bromide complexes containing SSBn and an extended network containing [Cu4I4] clusters bridged by the SSBn were formed for the corresponding copper‒iodide complex for the latter ligand. The coordination and structural features of the two bis-thione ligands are discussed.

Anticancer activity of a series of copper(II) complexes with tripodal ligands

A series of copper(II) complexes with tripodal polypyridylamine ligands (derived from the parent ligand tris(2-pyridylmethyl)amine, tmpa) has been synthesized. Crystallographic characterization was possible for all complexes obtained. The copper(II) chloride complexes were investigated for their in vitro anticancer potential using human tumor cell lines containing examples of cervical, colon, ovarian cancers and melanoma. Some compounds showed a similar activity compared to that of cisplatin, however no systematic behavior could be observed.

New vinylpyridine anion exchangers for recovering thorium and nonferrous metals from nitric and hydrochloric acid solutions

The ability of new vinylpyridine anion exchangers of AXIONIT VPA series, produced by Axion—Rare and Noble Metals Joint-Stock Company (Russia), to take up Th from nitric acid solutions was studied. The static capacity of the sorbents for Th increases with increasing HNO3 concentration in the initial solution and reaches a maximum at 7–8 M HNO3. The sorbed Th can be completely desorbed with dilute HNO3 solutions. The stability of the sorption characteristics of the ion exchangers in multiple sorption–desorption cycles was evaluated. Vinylpyridine anion exchangers of AXIONIT VPA series well compete in the sorption and kinetic characteristics with VP-1Ap anion exchanger and can be successfully used for recovering Th and Pu from nitric acid solutions. Sorbents of the AXIONIT VPA series also take up copper and cobalt chloride complexes from hydrochloric acid solutions, which allows their use, e.g., for treatment of alkali metal chloride solutions to remove nonferrous metal impurities.

Non-innocent ligands in copper complexes catalyzed oxidation of thiols

ABSTRACT Copper(II) chloride complexes with nitrogen-containing ligands (amines, amides, heterocycles) were studied as catalysts of selective oxidation of thiols to disulfides. This process has an important biochemical analogue – the formation of disulfide bridge in proteins [Wang C, Wesener SR, Zhang H, Cheng Y-Q. An FAD-dependent pyridine nucleotide-disulfide oxidoreductase is involved in disulfide bond formation in FK228 anticancer depsipeptide. Chem and Biol. 2009;16:585–593]; which affects their activity [Zhang L, Chou CP, Moo-Young M. Disulfide bond formation and its impact on the biological activity and stability of recombinant therapeutic proteins produced by Escherichia coli expression system. Biotech Adv. 2011;29:923–929]. Also, thiol oxidation is an important process of oil sweetening. The search for effective and stable catalysts for this reaction is still topical [Ganguly SK, Das G, Kumar S, Sain B, Garg MO. Mechanistic kinetics of catalytic oxidation of 1-butanethiol in light oil sweetening. Catal Tod. 2012;198:246–251]. This article describes a mechanistic study of thiol oxidation and non-innocent ligands transformations during this reaction. The studied ligands are capable of oxidizing thiols, the reaction being followed by reoxidation of the reduced forms of the ligands with air oxygen. The oxidative activity of the ligand correlates with catalyst activity for thiol oxidation.

Synthesis and crystal structure of [chlorobis(triphenylphospino)(p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex

Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H1L) and triphenylphosphine in 1 : 1 : 2 molar ratio yielded complexes of stoichiometry, [CuX(η 1-S- H 1L)(Ph3P)2] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, 1H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) Å, b = 13.027(5) Å, c = 16.269(5) Å, α= 100.054(5) ∘, β= 99.228(5)∘ and γ= 97.234(5)∘. This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu2Cl2(μ 2-S-Hbtsc)2(Ph3P)2] ⋅2H2O. The intermolecular H-bonding, Cl ⋯HC ph, 2.733 Å and π interactions, {CHph⋯π, 2.796; 2.776 Å} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl ⋯HC ph, 2.896 Å H-bonding to form a 2D network. p-Chlorobenzaldehyde thiosemicarbazone formed tetrahedral monomeric complex 3 with copper(I) chloride in the presence of triphenylphospine. The intermolecular H-bonding, Cl⋯HCph, 2.733 Å and π interactions, {CHph⋯π, 2.796; 2.776 Å} in this complex led to the formation of 1D chain.

Palladium(ii) and copper(ii) chloride complexes bearing bulky α-diimine ligands as catalysts for norbornene vinyl-addition (co)polymerization

Palladium(ii) and copper(ii) chloride complexes bearing bulky 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine ligands were synthesized and sufficiently characterized by elemental and spectroscopic analysis along with X-ray diffraction analysis.

Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact.

The synthesis and co-ordination chemistry of a new 'bulky yet flexible' N-heterocyclic carbene ("IPaul") is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper(i) chloride complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*(OMe) complexes.

Effects of N,N-heterocyclic ligands on the in vitro cytotoxicity and DNA interactions of copper(ii) chloride complexes from amidino-O-methylurea ligands

Four novel copper(ii) complexes based on guanidine derivatives have been synthesized by addition of N,N-heterocyclic ligands, and their interesting biological activities have been evaluated.

An efficient and recyclable thiourea-supported copper(i) chloride catalyst for azide–alkyne cycloaddition reactions

We have shown that an air-stable bulky thiourea-supported copper(i) chloride complex is an efficient catalyst for the synthesis of five-membered heterocycles from alkynes and azides.

Synthesis, crystal structure, and electronic structure of a copper(II) chloride complex with 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone [Cu2(L-H)2Cl2

The [Cu2(L-H)2Cl2] compound (I) has been obtained by the reaction of 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone with copper(II) chloride. The crystal and molecular structure of I has been determined by X-ray crystallography. The L-H anion acts as a tridentate chelating ligand and is coordinated to the Cu atom through the O(1) atoms of the phenanthrenequinone moiety, the N(1) atom of the dihydroisoquinoline moiety, and the N(3) atom of the azo group to form two five-membered chelate rings. Complex I is a dimer with a double chloride bridge. The coordination polyhedron of the Cu atom is completed to a distorted pyramid by two chlorine atoms. The molecular and electronic structures of the L molecule and the model [Cu(L-H)Cl] complex have been determined by the density functional theory method. Spectroscopic characteristics of I have been determined.

Zn(II) and Cu(II) adsorption and retention onto iron oxyhydroxide nanoparticles: effects of particle aggregation and salinity.

BackgroundIron oxyhydroxides are commonly found in natural aqueous systems as nanoscale particles, where they can act as effective sorbents for dissolved metals due to their natural surface reactivity, small size and high surface area. These properties make nanoscale iron oxyhydroxides a relevant option for the remediation of water supplies contaminated with dissolved metals. However, natural geochemical processes, such as changes in ionic strength, pH, and temperature, can cause these particles to aggregate, thus affecting their sorption capabilities and remediation potential. Other environmental parameters such as increasing salinity may also impact metal retention, e.g. when particles are transported from freshwater to seawater.ResultsAfter using synthetic iron oxyhydroxide nanoparticles and nanoparticle aggregates in batch Zn(II) adsorption experiments, the addition of increasing concentrations of chloride (from 0.1 M to 0.6 M) appears to initially reduce Zn(II) retention, likely due to the desorption of outer-sphere zinc surface complexes and subsequent formation of aqueous Zn-Cl complexes, before then promoting Zn(II) retention, possibly through the formation of ternary surface complexes (supported by EXAFS spectroscopy) which stabilize zinc on the surface of the nanoparticles/aggregates. In batch Cu(II) adsorption experiments, Cu(II) retention reaches a maximum at 0.4 M chloride. Copper-chloride surface complexes are not indicated by EXAFS spectroscopy, but there is an increase in the formation of stable aqueous copper-chloride complexes as chloride concentration rises (with CuCl+ becoming dominant in solution at ~0.5 M chloride) that would potentially inhibit further sorption or encourage desorption. Instead, the presence of bidentate edge-sharing and monodentate corner-sharing complexes is supported by EXAFS spectroscopy. Increasing chloride concentration has more of an impact on zinc retention than the mechanism of nanoparticle aggregation, whereas aggregation condition is a stronger determinant of copper retention.ConclusionsBased on these model uptake/retention studies, iron oxyhydroxide nanoparticles show potential as a strategy to remediate zinc-contaminated waters that migrate towards the ocean. Copper retention, in contrast, appears to be optimized at an intermediate salinity consistent with brackish water, and therefore may release considerable fractions of retained copper at higher (e.g. seawater) salinity levels.

Steric influence of the 6-methyl group on the molecular and crystal structures of copper(II) chloride complexes with 2-(N-acetylamino)-6-methylpyridine

New coordination compounds of copper(II) chloride with 2-(N-acetylamino)-6-methylpyridine (L) of the compositions [Cu2L2Cl4] (1), [CuL(H2O)Cl2]·L (1a), and [CuL2Cl][CuLCl3]·C2H5OH (2) have been prepared by the reactions between ethanol solutions of L and ethanol solutions of CuCl2·2H2O at different Cu:L ratios. The compounds have been characterized by a set of methods including elemental analysis, IR-spectroscopy, single-crystal X-ray diffraction analysis, and magnetic susceptibility measurements in the range 5–300K (for 1). The crystal structures of 1 and 1a revealed distorted square-pyramidal geometry around Cu(II) centers, while in 2 both distorted square-pyramidal and trigonal–bipyramidal coordinations are present. L acts as a bidentate chelate ligand bound to the metal center through the pyridine N atom and the acetyl O atom. The results of the study demonstrate that the presence of 6-methyl substituent in L provides a high steric hindrance, precluding the formation of complexes with a distorted octahedral coordination of Cu(II).

Trace Amounts of Aqueous Copper(II) Chloride Complexes in Hypersaline Solutions: Spectrophotometric and Thermodynamic Studies

Knowledge of the thermodynamic properties of aqueous copper(II) chloride complexes is important for understanding and quantitatively modeling trace copper behavior in hydrometallurgical extraction processing. In this paper, UV–Vis spectra data of Cu(II) chloride solutions with various salinities (NaCl, 0–5.57 mol·kg−1) are collected at 25 °C. The concentration distribution of Cu–Cl species is in good agreement with those calculated by a reaction model (RM). The simple hydrated ion, Cu2+, is dominant at low concentration, whereas [CuCl]+, [CuCl2]0 and [CuCl3]− become increasingly important as the chloride concentration rises. Moreover, the RM calculation suggests the present of a small amount of [CuCl4]2−. The de-convoluted molar spectrum of each species is in excellent agreement with our previous theoretical results predicted by time-dependent density functional theory treatment of aqueous Cu-containing systems. The formation constants for these copper chloride complexes have been reported and are to be preferred, except log10 K 2 ([CuCl2]0).

Ferro- and antiferromagnetic coupling in a chlorido-bridged, tetranuclear Cu(ii) complex

A bispidine-like ligand involving four pyridine-N and three aliphatic-N donor atoms forms a bimetallic species with CuCl2 in which all seven N-donors are bound and which aggregates in the crystal through double chloride-bridging to give a tetranuclear unit. The magnetism of this solid can be interpreted in terms of a relatively weak antiferromagnetic coupling between the two Cu(ii) centres of the dinuclear subunits and a strong ferromagnetic coupling of the Cu(ii) centres in different dinuclear units involved in the bis-chlorido bridge. In solution, the assembly decays into the dinuclear subunits and, in agreement with the solid state studies, the interaction between the corresponding Cu(II) centres is shown to be primarily due to dipole-dipole coupling.

Raman and ab Initio Investigation of Aqueous Cu(I) Chloride Complexes from 25 to 80 °C

Temperature-dependent Raman studies of aqueous copper(I) chloride complexes have been carried out up to 80 °C, along with supporting ab initio calculations for the species [CuCl(n)(H2O)m](1-n), n = 0-4 and hydration numbers m = 0-6. Normalized reduced isotropic Raman spectra were obtained from perpendicular and parallel polarization measurements, with perchlorate anion, ClO4(-), as an internal standard. Although the Raman spectra were not intense, spectra could be corrected by solvent baseline subtraction, to yield quantitative reduced molar scattering coefficients for the symmetric vibrational bands at 297 ± 3 and 247 ± 3 cm(-1). The intensity variations of these bands with concentration and temperature provided strong evidence that these arise from the species [CuCl2](-) and [CuCl3](2-), respectively. The results from ab initio calculations using density functional theory predict similar relative peak positions and intensities for the totally symmetric Cu-Cl stretching bands of the species [CuCl2(H2O)6](-) and [CuCl3(H2O)6](2-), in which the water is coordinated to the chloride ions. A less intense Raman band at 350 ± 10 cm(-1) is attributed to the symmetric Cu-Cl stretching mode of hydrated species [CuCl(H2O)](0) with six waters of hydration. Temperature- and concentration-independent quantitative Raman molar scattering coefficients (S) are reported for the [CuCl2](-) and [CuCl3](2-)species.

DFT calculations and experimental FT-IR, dispersive-Raman and EPR spectral studies of Copper (II) chloride complex with 3-amino-1-methylbenzene

In this study, we present the synthesis and the characterization of Copper (II) chloride complex with 3-amino-1-methylbenzene (3A1MB). This complex was characterized by vibrational and EPR spectroscopic techniques and elemental analysis. The molecular structure and spectrometry of this complex: Cu(3A1MB)2Cl2 and its ligand: 3A1MB have been investigated theoretically by performing DFT/B3LYP calculations. Cu(3A1MB)2Cl2 has been optimized as two conformers and the more stable conformer is determined. The optimized geometries and calculated vibrational frequencies have been evaluated via comparison with experimental values, and the normal modes were assigned on the basis of the percent potential energy distribution (PED). A good agreement between calculated and experimental data is observed.