Reaction Of CuCl2 Research Articles

Syntheses and characterization of two 1D Cu(II) coordination polymers with 2,2′:6′,2″-terpyridine ligand

The solution reactions of CuCl2 with 2,2′:6′,2″-terpyridine (Terpy) and dicarboxylic acid (glutaric acid or suberic acid) afforded two 1D coordination polymers [Cu(Terpy)(C5H6O4)]n (I) and [Cu(Terpy)(C8H12O4)] · 3H2O (II) and their structures were characterized by IR, TG-DTA, and single-crystal X-ray diffraction. Crystallographic data for I: C20H16CuN3O4, Mr = 425.90, monoclinic, space group C2/c, a = 10.335(2), b = 21.193(4), c = 8.580(2) A, β = 111.99(3)°, V = 1742.5(6) A3, Z = 4, ρc = 1.623 g/cm3, F(000) = 872, R = 0.0304 and wR = 0.0915; and those for II: C23H29CuN3O7, Mr = 523.03, triclinic, space group P\(\bar 1\), a = 8.362(2), b = 10.605(2), c = 14.617(3) A, α = 73.26(3)°, β = 86.23(3)°, γ = 69.45(3)°, V = 1161.3(4) A3, Z = 2, ρc = 1.496 g/cm3, F(000) = 546, R = 0.0636 and wR = 0.1106. X-ray diffracion studies reveal that both complexes I and II feature 1D chain. The 1D polymer chains are connected by π-π-stacking interactions to generate 2D supramolecular layers.

Four new copper(II) complexes with di-substituted s-triazine-based ligands

In this paper, two di-substituted triazine-based ligands, 6-chloro-N,N,N′N′-tetrakis-pyridin-2-ylmethyl-[1,3,5]triazine-2,4-diamine (L1), and 6-chloro-N,N′-bis-pyridin-2-ylmethyl-N,N′-bis-thiophen-2-ylmethyl-[1,3,5]triazine-2,4-diamine (L2), have been prepared. Reaction of CuCl2·2H2O and Cu(NO3)2·3H2O with L1 and L2 results in the formation of [Cu2Cl4(L1)]·3MeOH (compound 1), [Cu4(NO3)8(L1)2]·2.07CH2Cl2·0.93MeOH (compound 2), [Cu2Cl4(L2)2] (compound 3) and [Cu(NO3)2(L2)]·CH2Cl2 (compound 4), respectively, which have been fully characterized and determined by single-crystal X-ray crystallography, FT-IR, elemental analysis, thermogravimetric measurement and magnetic susceptibility. The dinuclear compound 1 shows strong π–π interactions between the neighboring pyridine rings. The nitrate–π (1,3,5-triazine ring) interaction with the distance of 2.755Å in compound 2, is the closest contact reported so far. Compounds 3 and 4 are mononuclear copper(II) compounds, in which none of thiophene rings coordinates with copper(II) ion. In addition, the different orientations of two thiophene rings in compounds 3 and 4 lead to the π–π and CH2Cl2–π (thiophene ring) interactions in compound 4, but not in compound 3.

Bis(1-methylpiperazine-1,4-diium) tetrachloridocuprate(II)

The title compound, (C5H14N2)[CuCl4], was synthesized by hydro­thermal reaction of CuCl2 with 1-methyl­piperazine in an HCl/water solution. Both amine N atoms are protonated. The piperazine ring adopts a chair conformation. The Cu—Cl distances in the tetrahedral anion are in the range 2.2360 (7)–2.2732 (7) Å. In the crystal, moderately strong and weak inter­molecular N—H⋯Cl hydrogen bonds link the anion and cation units into an infinite two-dimensional network parallel to the ab plane.

Syntheses, Structures, and Properties of Trinuclear Copper(I)/Titanium(IV) Thiolate Complexes

AbstractThe thiolato‐bridged copper(I)/titanium(IV) complexes [Li(15‐crown‐5)thf]2[Cu2Ti(SPh)8] (thf = tetrahydrofuran) and [Cu2Ti(SPh)6(PPh3)2] have both been prepared in yields of at least 83 % by reaction of CuCl and TiCl4·2thf with LiSPh in THF in the presence of 15‐crown‐5 or PPh3, respectively. The crystal structures of the trinuclear compounds were determined by X‐ray analysis of single crystals. The dark colored compounds display absorption bands over a wide energy range with absorption onsets lying in the near infrared region at approximately 1350 nm for [Li(15‐crown‐5)thf]2[Cu2Ti(SPh)8] and 1050 nm for [Cu2Ti(SPh)6(PPh3)2]. Density functional calculations reproduce and explain the energy difference of the lowest energy transitions. Thermal treatment of [Cu2Ti(SPh)6(PPh3)2] up to 500 °C resulted in the cleavage of SPh2 and PPh3 and the formation of a mixture of ternary copper titanium sulfides, namely Cu4TiS4 and the defect thiospinel Cu0.33TiS2. In contrast, reflections of the powder diffraction patterns of the residues from the thermal analysis of [Li(15‐crown‐5)thf]2[Cu2Ti(SPh)8] could only be assigned to the known phases Cu1.8S (Digenite) and Cu1.96S (Djurleit).

Synthesis, structure, and photoluminescence properties of a novel 3D 3d-4f heterometallic polymer: Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (H2Bpdc = 2,2′-bipyridyl-5,5-dicarboxylic acid)

A novel 3D 3d–4f heterometallic polymer Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (I) (H2Bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) has been hydrothermally synthesized by the reaction of CuCl2 · 2H2O, PrCl3, H2Bpdc, TAA (TAA = 1H-tetrazolyl-1-acetic acid) and glacial acetic acid and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting heterometallic 3D coordination framework constructed from 2D praseodymium-oxygen layers and [Cu(Bpdc)2]3− and [CuCl(Bpdc)]2− pillars. The photofluorescence properties of I have been investigated.

Synthesis, structure and DFT calculation of a hexanuclear mixed-valence copper cluster supported by 2,3-disulfidobenzoate and 3-carboxybenzene-1,2-bis(thiolate)

A homoleptic hexanuclear Cu cluster, [(Cu(DSB)(CBT)) 2(Cu 2Br) 2][PPh 4] 2 ( 1-PPh 4 ) [DSB = 2,3-disulfidobenzoate; CBT = 3-carboxybenzene-1,2-bis(thiolate)] was synthesized as dark green crystals by the reaction of CuCl 2 with 2,3-dimercaptobenzoic acid in acetate buffer solution. The X-ray crystal study of 1-PPh 4 revealed its unique structural features: (1) one of two types of crystallographically distinct Cu centers adopted a square planer geometry and the other center had a tetrahedral geometry, and (2) intermolecular H-bonding interactions connected between carboxylic acid group of CBT and the carboxylate group of DSB led to the construction of an unprecedented topologic architecture of a zigzag patterned infinite sheet. In addition, taking into account the total charge of the molecule, which contained 2,3-disulfidobenzoate and 3-carboxybenzene-1,2-bis(thiolate), and the diamagnetic nature of 1-PPh 4 , 1-PPh 4 led to it is assignment as a mixed-valence Cu(I)/Cu(III) cluster. Such mixed valence states of Cu atoms were also examined by density functional theory calculation.

Bis(2-amino-6-methylpyridinium)trans-diaquabis(pyrazine-2,3-dicarboxylato)cuprate(II) hexahydrate

The title compound, (C6H9N2)2[Cu(C6H2N2O4)2(H2O)2]·6H2O, was obtained by the reaction of CuCl2·2H2O with pyrazine-2,3-dicarb­oxy­lic acid (pyzdcH2) and 2-amino-6-methyl­pyridine (2a-6mpy) in aqueous solution. The CuII atom is located on an inversion centre and has an overall octa­hedral coordination environment. Two N and two O atoms from (pyzdc)2− ligands define the equatorial plane and two water mol­ecules are in axial positions, resulting in a typical tetra­gonally Jahn–Teller-distorted environment. Extensive classical O—H⋯O, O—H⋯N and N—H⋯O and non-classical C—H⋯O hydrogen bonds, as well as π–π stacking inter­actions between aromatic rings of the cations [centroid–centroid distance = 3.58 (9) Å], lead to the formation of a three-dimensional supra­molecular structure.

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

AbstractThe reaction of CuCl2 with R2NCH2CH2NHC(Me)=CHCO(Me) [R = Me (HL1) or Et (HL2)] in the presence of Et3N leads to the formation of complexes [CuCl(Ln)] [n = 1 (1), 2 (2)]. Whereas the solid‐state structure of compound 2 is mononuclear with a close to square‐planar arrangement of the ClON2 donor set, compound 1 adopts a dinuclear di‐μ‐chlorido arrangement in which two mononuclear units having essentially the same arrangement as in 2 establish loose axial Cu···Cl interactions, each one of them with the Cl atom of the other one. Compounds 1 and 2 have been tested as reversible trapping agents for the controlled radical polymerization of styrene under a reverse atom‐transfer radical polymerization (ATRP) approach. Reversible Cl atom transfer leading to a controlled polymerization process is observed, although the controllability is negatively affected by slow radical trapping. A moderate effect on the polymerization rate, once all the radical initiator is consumed, was observed in the presence of an excess amount of pyridine (10 equiv. per Cu) and interpreted on the basis of the stabilization of the CuI system.

RETRACTED: Synthesis and characterization of chalcopyrite quaternary semiconductor Cu (InxGa1 − x) S2 nanowires by electrospun route

Abstract Chalcopyrite Cu(In 0.8 Ga 0.2 )S 2 (CIGS) nanowires were synthesized by using a relatively simple and convenient electrospun process. From the reactions of CuCl, InCl 3, GaCl 3 and thiocarbamide as a precursor, semiconductor CIGS nanowires with diameter in the range of 60–80 nm were obtained for Polyvinylbutyral/CIGS precursor ratios of 40% at an applied voltage of 25 kV after annealing treatment at 600 °C for 3 h. A probable formation mechanism of chalcopyrite quaternary semiconductor nanowires is proposed based on a series of comparative experiments conducted under various reaction conditions.

Reversible switching of copper(ΙΙ) complexes using a hemilabile N,N′-Bis(β-carbamoylethyl)trans-1,2-diaminocyclohexane ligand

The reaction of CuCl 2 ·2H 2 O with one equivalent hemilabile diaminodiamide ligand N,N′-bis(β-carbamoylethyl)trans-1,2-diaminocyclohexane ( 1 ) gave a blue compound [Cu(C 12 H 24 N 4 O 2 )Cl]Cl·H 2 O ( 2 ). With more than one equivalent ligands, 2 was transformed to a purple species [Cu(C 12 H 22 N 4 O 2 )]·3H 2 O ( 3 ) by the Cu―O to Cu―N bond rearrangement at two amide sites of the complex. Compounds 2 and 3 are structurally switchable in response to the Cu(II)/ 1 ratios in an aqueous solution. Structures of 2 and 3 were characterized by single-crystal X-ray diffraction analysis. Structural data for 2 indicated that the copper atom adopts a five-coordinated N 2 O 2 Cl environment and gives a square-pyramidal geometry. The structure of 3 showed that the copper atom adopts a four-coordinated N 4 environment, giving a distorted square-planar geometry. The color change could be described as a pH dependent isomerization of the ligand. The results presented could be useful in the design of new Cu(II)-based switching materials.

Unexpected multiple bond cleavage and rearrangement of organosulfide ligands in the presence of Cu(ii) assisted by solvothermal and solvothermal-microwave conditions

An unprecedented in situ multiple bond cleavage of S-S, S-C(sp(2)) and C-N in the pyrimidinedisulfide (pym(2)S(2)) ligand is observed by the reaction of CuCl(2)·2H(2)O with this ligand under solvothermal and solvothermal-microwave conditions. In this process the formation of the compound [Cu(II)(μ-Cl)(Cl)L](2), where L represents the new ligand (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde), is observed. This ligand has been further isolated and X-ray characterized. The similar reaction carried out under solvothermal-microwave conditions gives, in addition to the latter compound, the complex {9·[Cu(pym(2)S(3))(μ-Cl)(Cl)](2)·[Cu(pym(2)S(2))(μ-Cl)(Cl)](2)}. Coordination of a pyrimidinetrisulfide ligand (pym(2)S(3)) is reported for the first time. This work represents an illustrative example of the novel synthetic perspectives attainable via solvothermal-microwave procedures.

Nitroimidazole and glucosamine conjugated heteroscorpionate ligands and related copper(ii) complexes. Syntheses, biological activity and XAS studies

New nitroimidazole and glucosamine conjugated heteroscorpionate ligands, namely 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide (L(MN)) and 1,3,4,6-tetra-O-acetyl-2-{[bis(3,5-dimethyl-1H-pyrazol-1-yl)acetyl]amino}-2-deoxy-β-D-glucopyranose (L(DAC)), respectively, were synthesized by direct coupling of preformed side chain acid and amine components. The related copper(II) complexes {[(L(MN))(2)Cu]Cl(2)}, and {[(L(DAC))(2)Cu]Cl(2)} have been prepared from the reaction of CuCl(2)*2H(2)O with L(MN) or L(DAC) ligand in methanol solution. Single crystal structural characterization was undertaken for the L(MN) ligand. In the absence of a coordinated metal core, the overall arrangement of the ligand is determined by some loose intra- and inter-molecular nonbonding contacts. X-Ray Absorption Spectroscopy (XAS) has been used to probe the local structure of the two copper(II) complexes, {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)}. The EXAFS analysis has permitted the identification of the local environment of the copper site. Copper interacts with 2 units of ligand in both complexes, and it is found to be 6-fold coordinated. Its local structure is described by four Cu-N and two Cu-O interactions to form a pseudo-octahedron core, with a 0.14 Å lengthening of the Cu-O bond length in the case of L(DAC) complex with respect to the L(MN) one, likely due to the higher steric hindrance of the glucosamine moiety. The XANES analysis agrees with these results, also confirming the Cu(II) formal copper oxidation state for both complexes. The new copper(II) complexes {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)} as well as the corresponding uncoordinated ligands were evaluated for their cytotoxic activity towards a panel of several human tumour cell lines. The results reported here indicate that both copper(II) complexes show similar spectra of cytotoxicity and very low resistance factors (RF < 2) against C13* ovarian cancer cells which have acquired resistance to cisplatin.

Plasma Electrochemistry in 1‐Butyl‐3‐methylimidazolium dicyanamide: Copper Nanoparticles from CuCl and CuCl2

AbstractWe report on the reaction of CuCl and CuCl2, each dissolved in 1‐butyl‐3‐methylimidazolium dicyanamide ([BMIm]dca), with a glow discharge argon plasma. The interaction of the plasma with the solutions exhibits a strong reaction with gas evolution and the growth of copper nanoparticles. The particle size was determined with transmission electron microscopy (from the particle/ionic liquid, IL solution). The chemical composition was investigated by ex situ X‐ray photoelectron spectroscopy (XPS). We found that the mean diameter of the copper particles produced in CuCl/[BMIm]dca and CuCl2/[BMIm]dca was in the same order of magnitude (between 2 and 10 nm). Despite the strong reaction we found no hints for IL degradation products in the liquids with infrared spectroscopy. XPS showed that ex situ treatment of the particles leads to the formation of CuO. magnified image

2-Hydroxy-N'-(4-oxo-4-phenyl-butan-2-yl-idene)benzohydrazidato(2-)]pyridine-copper(II).

The mononuclear title complex, [Cu(C17H14N2O3)(C5H5N)], was synthesized by the reaction of CuCl2·2H2O with N-(4-oxo-4-phenyl­butan-2-yl­idene)benzohydrazide (H2 L). The central CuII atom exhibits a distorted square-planar coordination geometry, defined by two O atoms, one N atom from the ligand and one pyridine N atom with Cu—N distances of 1.874 (4) and 1.963 (4) Å, while the Cu—O distances are 1.857 (3) and 1.890 (3) Å. An intra­molecular O—H⋯N inter­action occurs.

Metal to Ligand Interactions and Hydrogen Bonding in the Design of Metallosupramolecular Compounds: Effect of pH and Aprotic Solvents on the Nature of Materials Based on Bis(4-pyridylthio)methane and Copper(II) Chloride

The ligand 4bpytm [4bpytm = bis(4-pyridylthio)methane] in strongly acidic media afforded H24bpytm(NO3)2. The reaction of CuCl2.2H2O with 4bpytm at low pH values afforded three supramolecular compounds: H24bpytm[CuCl4] (1) and the monomeric complexes [CuCl3(H4bpytm)(4bpytm)] (2) and [CuCl2(H4bpytm)2]·Cl2 (3). Nevertheless, the same reaction using aprotic solvents under microwave irradiation afforded the 1D coordination polymers [CuCl2(4bpytm)]·2dmf (4.dmf) and [CuCl2(4bpytm)]·2dmso (4.dmso). The 3D supramolecular organization through weak interactions has been analyzed for all of the compounds, and their thermal behavior and structural dynamics after solvent release were also investigated for 4.dmf and 4.dmso. X-ray structural analysis of these complexes showed that the synthetic conditions used represent an effective method to obtain metal−organic square grid networks with cavities.

Effect of the condition of synthesis on the composition and structure of copper(II) complexes with benzimidazole

The composition and structure of copper(II) benzimidazole complexes obtained by the reaction of CuCl2 with benzimidazole (BIm) were determined. At pH 4.5–5.5, depending on the reactant ratio, dimeric compounds with the composition Cu(BIm)4Cl2 · 2H2O and Cu(BIm)2Cl2 · H2O are formed. They are converted to monomers at about 200°C. At pH > 8, irrespective of the reactant ratio, the polymer (Cu(OH)L)n is formed. The complexation of copper(II) with benzimidazole in water and aqueous dioxane was studied by potentiometry, and the stability constants of the complex compounds and their dependence on the solvent composition were determined.

Synthesis, characterization, and crystal structure determination of two copper(II) complexes: [Cu(dm4bt)Cl2(DMSO)] and [{Cu(dm4bt)(H2O)(tpht)} · H2O] n

Copper complexes, [Cu(dm4bt)Cl2(DMSO)] (1) and [{Cu(dm4bt)(H2O)(tpht)} ⋅ H2O] n (2) (dm4bt, 2,2′-dimethyl-4,4′-bithiazole; tpht, terephthalate), have been synthesized and their crystal structures were determined by X-ray crystallography. Complex 1 was prepared from a reaction of CuCl2 ⋅ 2H2O with dm4bt and terephthalic acid in a mixture of methanol, water, and DMSO. Complex 2 was prepared from a reaction of CuCl2 ⋅ 2H2O with dm4bt, terephthalic acid, and ethylene diamine in a mixture of methanol and water. The two complexes were characterized by IR, UV-Vis spectroscopy, and single-crystal structure. Complex 2 was also characterized by electron paramagnetic resonance spectra. Complex 1 is a monomer while 2 is a coordination polymer. This copper tpht polymer has a cis-configuration of tpht rings opposed to zigzag chains with anti-configuration usually reported in the literature.

Synthesis and Structural Flexibility of a Series of Copper(II) Azolate‐Based Metal–Organic Frameworks

AbstractThe reaction of CuCl2·2H2O with three novel ditopic ligands, 2‐methyl‐1,4‐benzeneditetrazolate (MeBDT2–), 4,4′‐biphenylditetrazolate (BPDT2–), and 2,3,5,6‐tetrafluoro‐1,4‐benzeneditriazolate (TFBDTri2–), affords the metal–organic frameworks Cu(MeBDT)(dmf) (1), Cu(BPDT)(dmf) (2), and Cu(TFBDTri)(dmf) (3), respectively. These materials feature a common network topology in which octahedral Cu2+ ions are bridged by azolate ligands and dmf molecules to form one‐dimensional chains. The individual chains are connected by the organic bridging units to form diamond‐shaped channels, in which the solvent molecules project into the pores. The bridging dmf molecules in 1 are readily displaced by other coordinating solvent molecules, which leads to a change in the pore dimensions according to the steric bulk of the solvent. Interestingly, attempts to exchange the analogous solvent molecules in the expanded framework 2 induced no change in the pore size, revealing the rigidity of the framework. Meanwhile, 3 exhibits modest flexibility and an improved thermal stability consistent with its chemical functionality. The marked difference in flexibility highlights the considerable impact the organic linker can have on the dynamic framework properties.

ChemInform Abstract: Novel Sandwiched Intermetallic Selenoantimonates: Soft Synthesis and Characterization of Cu2SbSe3×0.5en and Cu2SbSe3×en.

Two novel two-dimensional (layered) intermetallic copper selenoantimonates Cu2SbSe3·0.5en (I) and Cu2SbSe3·en (II), have been prepared by soft solvothermal reactions of CuCl, SbCl3, and Se with A2Se (A = Na, K) in the presence of ethylenediamine. Single-crystal X-ray diffraction analyses show that both structures crystallize in the monoclinic crystal system. Compound I belongs to the P21/n (no. 14) space group with a = 6.399(1) A, b = 18.858(4) A, c = 6.786(1) A, β = 113.23(3)°, Z = 4, V = 752.5(2) A3, and II belongs to the Pn (no. 7) space group with a = 6.321(2) A, b = 11.841(2) A, c = 6.932(2) A, β = 111.59(2)°, Z = 2, V = 482.4(2) A3. Both compounds consist of Cu2SbSe3 layers separated by free ethylenediamine molecules. The intermetallic layers are very similar in I and II, but the orientations of the solvent molecules are different. Both compounds contain copper atoms of mixed-valence, Cu(I) and Cu(II), and both are semiconductors with intermediate band gaps (∼1.6 eV).

ChemInform Abstract: Synthesis, Structural Characterization, and Theoretical Calculations of a New Copper(I)-Octahydrotriborate Complex.

Reactions of CuCl with [R4N][B3H8] (R = Et, n-Pr, n-Bu) salts give the new [R4N][ClCuB3H8] complexes of copper(I). These compounds have fluxional behavior in solution. MP2 and DFT calculations show that the most stable conformation of the anion has two boron atoms bound to the metal by two B−H−Cu bridge hydrogen bonds.