Insights into the extraction mechanism from the coordination chemistry of copper(II) with a synergistic mixture which mimics Versatic10 and 2-ethylhexyl 4-pyridinecarboxylate ester

In the present work, a copper(II) synergist complex with methyl isonicotinate (L^I, a short chain analog of 2-ethylhexyl 4-pyridinecarboxylate ester) and isobutyric acid (HB^I, a short chain analog of Versatic10) was synthesized and studied by X-ray single-crystal diffraction. The results indicated that the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate crystallizes in the monoclinic C2/c space group and confirmed the composition [Cu(B^I)₂(L^I)]₂. The crystal structure consisted of centrosymmetric dimeric units, in which the two Cu ions are bridged in pairs by four carboxylate groups of the deprotonated isobutyric acid. In order to bridge the gap between the solid-state structure of the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate and the solution structure of the extracted copper(II) complex in the non-polar organic phase, the two copper(II) complexes were further investigated by Fourier transform infrared spectroscopy (FT-IR) and electrospray ionization mass spectrometry (ESI-MS). The results indicated that the extracted copper(II) complex in the non-polar organic phase has a similar coordination structure as the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate.     

Structural Insights into the Coordination and Extraction Mechanism of Nickel(II) with Dinonylnaphthalene Sulfonic Acid and n‐Hexyl 3‐Pyridinecarboxylate Ester as Extractants

In this work, a nickel(II) synergist complex with methyl isonicotinate (B^I, a short chain analog of n‐hexyl 3‐pyridinecarboxylate ester) and naphthalene‐2‐sulfonic acid (HNS, a short chain analog of dinonylnaphthalene sulfonic acid) was synthesized and studied by single‐crystal X‐ray diffraction. The nickel(II) complex crystallizes in the monoclinic P 2₁/n space group with the composition [Ni(H₂O)₄(B^I)₂](NS)₂·2H₂O. The Ni(II) ions of these crystallographically independent molecules lie on an inversion center, forming a trans‐form distorted octahedral coordination structure. The nickel(II) ions can coordinate with four water molecules and two B^I ligands, resulting in a mono‐metallic structure [Ni(H₂O)₄(B^I)₂]²⁺. There is no direct interaction between nickel(II) and sulfonic oxygen atoms of the sulfonate anions, but hydrogen bonds form between sulfonic oxygen atoms and water molecules in the synergist complex. In order to further elucidate the solution structure of the nickel(II) complexes with the actual synergistic mixture containing n‐hexyl 3‐pyridinecarboxylate ester and dinonylnaphthalene sulfonic acid in the nonpolar organic phase, the nickel(II) complexes were studied by electrospray ionization mass spectrometry. The results indicated that the extracted nickel(II) complexes in the nonpolar solvent have a similar coordination structure as that of the crystalline nickel(II) synergist complex.     

Structure of iron (II) and cobalt (II) bromide complexes in aqueous solution by X-ray diffraction analysis

Structures of bromo-metal complexes in concentrated aqueous solutions of FeBr₂ and of CoBr₂ were investigated by X-ray diffraction analysis. The complexes possess an octahedral geometry coordinating Br^– along with H₂O ligands. The frequency factors of metal-Br contacts per one atom of metal were 0.325 for the 2.7M (mol-dm^–3) and 0.747 for the 4.5M FeBr₂ solutions, and 0.280 for the 2.8M and 0.595 for the 4.3M CoBr₂ solutions. The frequency factors suggested that the tendency of metal ions to forming monobromo complexes is in the order, Fe>Co>Ni相似文献   

Structures and fragmentations of cobalt(II)-cysteine complexes in the gas phase

The electronebulization of a cobalt(II)/cysteine(Cys) mixture in water/methanol (50/50) produced mainly cobalt-cationized species. Three main groups of the Co-cationized species can be distinguished in the ESI-MS spectrum: (1) the cobalt complexes including the cysteine amino acid only (they can be singly charged, for example, [Co(Cys)n- H]+ with n = 1-3 or doubly charged such as [Co + (Cys)2]2+); (2) the cobalt complexes with methanol: [Co(CH3OH)n- H]+ with n = 1-3, [Co(CH3OH)4]2+; and (3) the complexes with the two different types of ligands: [Co(Cys)(CH3OH) - H]+. Only the singly charged complexes were observed. Collision-induced dissociation (CID) products of the [Co(Cys)2]2+, [Co(Cys)2 - H]+ and [Co(Cys) - H]+ complexes were studied as a function of the collision energy, and mechanisms for the dissociation reactions are proposed. These were supported by the results of deuterium labelling experiments and by density functional theory calculations. Since [Co(Cys) - H]+ was one of the main product ions obtained upon the CID of [Co(Cys)2]2+ and of [Co(Cys)2 - H]+ under low-energy conditions, the fragmentation pathways of [Co(Cys) - H]+ and the resulting product ion structures were studied in detail. The resulting product ion structures confirmed the high affinity of cobalt(II) for the sulfur atom of cysteine.     

Metal(II)-promoted hydrolysis of pyridine-2-carbonitrile to pyridine-2-carboxylic acid. The structure of [Cu(pyridine-2-carboxylate)2] · 2H2O

Pyridine-2-carbonitrile (2-CNpy) undergoes Cu(II) or Co(II)-promoted hydrolysis to pyridine-2-carboxamide (piaH) and/or pyridine-2-carboxylic acid (pycH). The pathway of pycH formation depends on the presence of 2-amino-2-hydroxymethyl-1,3-propanediol (AL¹) and on the central atom. In the absence of AL¹, Co(II) or Cu(II) ions mediate piaH formation under mild reaction conditions in the first hydrolytic step. Cu(II) ions assist in piaH transformation to pycH by subsequent reflux. In the presence of AL¹ and Co(II), a Co(II) complex containing pyoxaL¹ (2-(2-pyridinyl)-4,4-bis(hydroxymethyl)-2-oxazoline) is formed in the first stage; subsequent decomposition of pyoxaL¹ under the reflux yields pycH. Under similar conditions, no solid Cu(II) complex with pyoxaL¹ can be isolated, but a Cu(II) complex with coordinated pyc⁻ anions precipitates from the reaction mixture. The synthesis, spectral and magnetic properties of the complexes [Co(H₂O)₂ (piaH)₂]Cl₂, [Co(H₂O)₂(pyc)₂] · 2H₂O, [Cu(H₂O)₂(piaH)₂]Cl₂, [Cu(pyc)₂] and [Cu(pyc)₂] · 2H₂O, including the structure determination of the latter one, are described.     

Synthesis and structural characterisation of cobalt(II) and iron(II) chloride complexes containing bis(2-pyridylmethyl)amine and tris(2-pyridylmethyl)amine ligands

Treatment of (2-C₅H₄N)CH_{2 3}N (TPA) with one equivalent of MCl₂ in n-BuOH at elevated temperatures affords the six-coordinate complexes [(TPA)MCl₂] (M = Co (1), Fe (2)) and, in the case of CoCl₂, the five-coordinate chloride salt [(TPA)CoCl]Cl (3). Conversely, addition of an excess of CoCl₂ in the latter reaction leads to [(TPA)CoCl]₂[CoCl₄] (4) as the only isolable product. Interaction of one equivalent of (2-C₅H₄N)CH_{2 2}NH (DPA) and MCl₂ under similar reaction conditions to that described above affords the dimeric species [(fac-DPA)MCl(μ-Cl)]₂ (M = Co (5), Fe (6)), while the bis(ligand) halide salts [(fac-DPA)₂M]Cl₂ (M = Co (7), Fe (8)) are accessible on addition of two equivalents of DPA. In the presence of air, 6 undergoes oxidation to give [ (fac-DPA)FeCl_{2 2}(μ-O)] (9). Single-crystal X-ray diffraction studies are reported for 1, 2 · MeCN, 3, , 7 · 3MeCN, 8 · 3MeCN and 9.     

Separation of cobalt(II) from nickel(II) by solid-phase extraction into Aliquat 336 chloride immobilized in poly(vinyl chloride)

A solid-phase absorbent obtained by the immobilization of Aliquat 336 chloride in poly(vinyl chloride) is reported to extract preferentially Co(II) from its 7 M hydrochloric acid solutions containing Ni(II). Under the experimental conditions there was no extraction of Ni(II) which allowed the complete separation of these two ions. Co(II) was rapidly and quantitatively back-extracted with deionised water. A mechanism for the extraction of Co(II) is proposed based on the formation of the ion-pair A⁺[HCoCl₄]⁻ where A⁺ is the Aliquat 336 cation. Fe(III) and Cd(II), usually present in Co(II) and Ni(II) samples, were also extracted into the solid-phase absorbent though at a slower rate than Co(II) and they did not interfere with the separation of Co(II) from Ni(II). It was also demonstrated that this approach allowed the complete separation of Ni(II) from the other metal ions mentioned above.     

Crystal structure of tris[(2.2.2-cryptand)× (nitrato-O,O′)lead(II)] pentakis(nitrato-O,O′)lead(II)

A novel coordination compound tris[(2.2.2-cryptand)(nitrato-O,O′)lead(II)] pentakis(nitrato-O, O′)lead(II), 3[Pb(NO₃)(Crypt-222)]⁺·[Pb(NO₃)₅]^3? (I) has been prepared and studied by the single crystal X-ray diffraction technique. The crystals of I are monoclinic: space group Pc, a = 25.944 Å, b = 18.389 Å, c = 17.145 Å, β = 93.33°, Z = 4. The structure of I has been solved by the direct and heavy atom methods and refined in a full-matrix anisotropic-isotropic approximation to R = 0.122 for the total of 11145 measured reflections (automated diffractometer CAD-4, λMoK _α). The structure of I includes six independent host-guest complex cations [Pb(NO₃)(Crypt-222)]⁺ and two independent complex anions [Pb(NO₃)₅]^3?. Coordination number of the cation Pb²⁺ equals ten in all these complex ions, and its coordination polyhedron in the first of them is a strongly distorted “hexagonal bipyramid” with two forked vertices, while for the latter ones it is a strongly distorted “square pyramid” with all five vertices forked.     

Dinuclear cobalt(II) complexes with double phosphate ester bridges and tetradentate ligands having anisole or quinoline appendages

Phosphate esters provide a rigid and stable polymeric backbone in nucleic acids. Metal complexes with phosphate ester groups have been synthesized as structural and spectroscopic models of phosphate‐containing enzymes. Dinucleating ligands are used extensively to synthesize model complexes since they provide the support required to stabilize such complexes. The crystal structures of two dinuclear Co^II complexes, namely bis(μ‐diphenyl phosphato‐κ²O :O ′)bis({2‐methoxy‐N ,N‐bis[(pyridin‐2‐yl)methyl]aniline‐κ⁴N ,N ′,N ′′,O }cobalt(II)) bis(perchlorate), [Co(C₁₂H₁₀O₄P)₂(C₁₉H₁₉N₃O)₂](ClO₄)₂, and bis(μ‐diphenyl phosphato‐κ²O :O ′)bis({N ,N‐bis[(pyridin‐2‐yl)methyl]quinolin‐8‐amine‐κ⁴N ,N ′,N ′′,O }cobalt(II)) bis(perchlorate), [Co(C₁₂H₁₀O₄P)₂(C₂₁H₁₈N₄)₂](ClO₄)₂, with tetradentate 2‐methoxy‐N ,N‐bis[(pyridin‐2‐yl)methyl]aniline (L ¹) and N ,N‐bis[(pyridin‐2‐yl)methyl]quinolin‐8‐amine (L ²) ligands are reported. The complexes have similar structures, with distorted octahedral geometries around the metal centres. Both are centrosymmetric (Z ′ = 0.5), with the Co^II centres doubly bridged by diphenyl phosphate ester groups. A number of aromatic–aromatic interactions are present and differ between the two complexes as the anisole group in L ¹ is replaced by a quinoline group in L ². A detailed study of these interactions is presented.     

Binding sites of [Ru(bpy)2(H2O)2](BF4)2 with sulfur- and histidine-containing peptides studied by electrospray ionization mass spectrometry and tandem mass spectrometry

The composition and binding sites of cis-[Ru(II)(bpy)2]2+-bound sulfur-containing peptides of Met-Arg-Phe-Ala, glutathione and oxidized glutathione, and also histidine-containing peptide of oxidized insulin B chain, were investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). The composition of Ru(II)-containing peptides was precisely determined by ESI-MS, zoom scan and simulation of isotope distribution patterns. MS/MS analysis shows that, in sulfur-containing peptides, the Ru(II) complex prefers to anchor to a carboxyl group, although some other potential binding sites of thiol, thioether and N-terminal amino groups present in these peptides, and in oxidized insulin B chain, Ru(II) first anchors to His10, then either to the hydroxyl group of Thr27 or to the carboxyl group of Ala30. Its secondary structure and microenvironment surrounding the potential binding sites may affect the binding ability of cis-[Ru(II)(bpy)2]2+ to oxidized insulin B chain.     

Syntheses,characterizations, crystal structures,antibacterial and SOD-like activities of nickel(II) and copper(II) complexes with 2-((Z)-(4-methoxyphenylimino)methyl)-4,6-dichlorophenol

Three mononuclear nickel(II) and copper(II) complexes, [Ni(L)₂(py)₂] (1), [Ni(L)₂(DMF)(H₂O)] (2), and [Cu(L)₂] (3), where HL = 2-((Z)-(4-methoxyphenylimino)methyl)-4,6-dichlorophenol, py = pyridine and DMF = N,N-dimethylformamide, have been synthesized and their structures determined by single crystal X-ray analysis. Complexes 1–3 crystallized in the monoclinic system of the space groups C2/c, P2_1/n, and P2_1/c, respectively. The crystal structures of 1 and 2 present an octahedral geometry at the metal center and 3 shows a square-planar geometry. The FT-IR spectra, UV–vis spectra, and magnetic susceptibility measurements agree with the observed crystal structures. EPR spectra indicate a d_x2–y2 ground state (g_|| > g_⊥ > 2.0023 and A_|| > A_⊥) for 3 at RT and LNT. The results of simultaneous TG-DTA analyses of 1 and 3 showed the final degradation products are NiO for 1 and CuO for 3. The Schiff base (HL) behaves as monobasic bidentate ligand possessing N and O donor atoms. Electrochemical properties for the complexes are similar and involve two irreversible redox processes. Complex 3 exhibits the ability to inhibit jack bean urease, although its Schiff base has no ability to inhibit urease. Complex 1 exhibits more active scavenging effects against O₂^? than HL, 2 and 3 under the same conditions. Antibacterial screening activities of these complexes were also investigated.     

The effect of diluents on extraction of copper(II) with di(2-ethylhexyl)phosphoric acid

The liquid–liquid extraction of copper(II) from sulfate medium with di(2-ethylhexyl)phosphoric acid (D2EHPA, HL) at 25°C is studied with the following parameters: pH, concentration of the extractant, and the nature of diluent. The effect of the diluent using polar and nonpolar solvents in the extraction of copper(II) is discussed. The extracted copper(II) species were CuL₂ in 1-octanol and methyl isobutyl ketone and CuL₂ · 2HL in toluene, carbon tetrachloride, and cyclohexane. The extraction constants are evaluated for different diluents.     

A thermal decomposition study on cobalt(II) complexes of 1,2-bis(IMINO-4'-antipyrinyl)ethane

The phenomenological, kinetic and mechanistic aspects of thermal decomposition of perchlorate, nitrate, chloride, bromide and iodide complexes of cobalt(II) with the Schiff base 1,2-bis(imino-4'-antipyrinyl)ethane (GA) have been studied by TG and DTG analyses. The kinetic parameters like the activation energy, pre-exponential factor and entropy of activation were calculated. The decomposition reactions follow 'random nucleation with one nucleus on each particle - Mampel model'. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone

An interesting series of nine new copper(II) complexes [Cu₂L₂(OAc)₂]·H₂O (1), [CuLNCS]·½H₂O (2), [CuLNO₃]·½H₂O (3), [Cu(HL)Cl₂]·H₂O (4), [Cu₂(HL)₂(SO₄)₂]·4H₂O (5), [CuLClO₄]·½H₂O (6), [CuLBr]·2H₂O (7), [CuL₂]·H₂O (8) and [CuLN₃]·CH₃OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the d_x²-y² orbital. The structure of the compound, [Cu₂L₂(OAc)₂] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P2₁/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.     

Solid phase extraction of zinc(II) using a PVC-based polymer inclusion membrane with di(2-ethylhexyl)phosphoric acid (D2EHPA) as the carrier

A polymer inclusion membrane (PIM) is reported consisting of 45% (m/m) di(2-ethylhexyl)phosphoric acid (D2EHPA) immobilized in poly(vinyl chloride) (PVC) for use as a solid phase absorbent for selectively extracting Zn(II) from aqueous solutions in the presence of Cd(II), Co(II), Cu(II), Ni(II) and Fe(II). Interference from Fe(III) in the sample is eliminated by precipitation with orthophosphate prior to the extraction of Zn(II). Studies using a dual compartment transport cell have shown that the Zn(II) flux (2.58 × 10⁻⁶ mol m⁻² s⁻¹) is comparable to that observed for supported liquid membranes. The stoichiometry of the extracted complex is shown to be ZnR₂·HR, where R is the D2EHPA anion.     

Structure and electrospray mass spectrometry studies on dithiacyclooctan-3-ol-containing palladium (II) complex of trans -[Pd(dtco-3-OH)_2](ClO_4)_2·2DMSO

The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group pi, a = 0.7077(2) nm, b = 1.0788(1) nm, c = 1.1111(1) nm, α=67.710(8)°, β = 73. 59(2)°, γ = 85. 39(2)°,R1 = 0 . 0368 and Rw = 0.0998. The palladium (II) is coordinated by four sulfur atoms with a regular square planar configuration. The Pd-S distances are 0.2314(1) and 0.2317(1) nm, respectively. Both dtco-3-OH ligands are in the boat-chair configuration and two hydroxyl groups are on the opposite sites of the PdS4 coordination plane and are towards Pd(II). The Pd-O distance is 0. 285 nm, indicating a weak interaction between them. A typical hydrogen bond between the hydroxyl group of dtco-3-OH ligand and DMSO was observed in the crystal structure. An aqueous solution prepared with the crystals of the complex was used for the investigation of electrospray mass spectrometry ( ESMS ). Besid     

Synthesis,spectral characterization and crystal structure of copper(II) complexes of 2-hydroxyacetophenone-N(4)-phenyl semicarbazone

Six new copper(II) complexes of 2-hydroxyacetophenone-N(4)-phenyl semicarbazone have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on EPR studies, the spin Hamiltonian and bonding parameters have been calculated. The g   values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the d_x2-y2${\text{d}}_{x^2-y^2}$ orbital. The metal–ligand bonding parameters evaluated showed strong in-plane σ and in-plane π-bonding. The structure of the compound, CuLphen has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed a monoclinic lattice with space group symmetry P2₁/c. The compound adopts a distorted square pyramidal geometry with a N₂O₂ core as the base.     

Synthesis and crystal structure of polymer cobalt(II) complex, 1,2,4,5-benzenetetracarboxylate hexaimidazole tetraaqua cobalt (II) tetrahydrate

The crystal structure of the title complex {[Co(TCB)2/2-(IMI)2(H2O)2][Co(IMI)4(H2O)2] } (H2O)4 (where TCB = 1,2,4,5-benzenetetracarboxylic anion; IMI = imidazole) has been determined by X-ray diffraction method. Crystal data for {[Co(TCB)2/2(IMI)2(H2O)2][Co(IMI)4(H2O)2]}-(H2O)4: triclinic, space group P 1, a = 1.0647(2) nm, b = 1.1165(1)nm,c = 1.00361(1)nm,α = 91.56(1)°,β = 111.34(1)°, γ = 115.642(10)°, V = 0.9772(3) nm5, Z = 1. The polymer cobalt (II) complex has a novel three-dimension network structure. Co(1) atom and Co(2) atom both are coordinated in an octahedral arrangement and located in the center of the coordination anion and the center of the coordination cation, respectively. Moreover four carboxyl groups of TCB are divided into two types, two para-carboxyl groups bridge Co(1) atom in monodentate fashion and other two para-carboxyl groups are in free.     

Structural, theoretical and multinuclear NMR study of mercury(II) complexes with a new ambidentate phosphorus ylide

The reaction of the new ambidentate ylide, Ph₃PCHCOCH₂COOC₂H₅ (EAPPY), with HgX₂ (X = Cl, Br and I) in equimolar ratios using methanol as the solvent leads to binuclear complexes of the type [EAPPY·HgX₂]₂ (X = Cl (1), Br (2) and I (3)). Single crystal X-ray analysis reveals the presence of a centrosymmetric dimeric structure containing the ylide and HgX₂ (X = Br or I)_. The IR and NMR data of the product [(EAPPY)·HgCl₂]₂ (1), formed by the reaction of mercury(II) chloride with the same ylide, are similar to those of 2 and 3. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in each of the three products. Theoretical studies indicate that the nature of the R group in ylides of the type Ph₃PCHCOR has a weak effect on the Hg-C(ylide) bond length in binuclear Hg₂L₂I₄ complexes.     

Nickel(II) and cobalt(II) complexes of methyl(2-aminocyclopentene-1-dithiocarboxy)-S-acetate (ACDASAMe)

Nickel(II) and cobalt(II) bis-chelates of methyl(2-aminocyclopentene-1-dithiocarboxy)-S-acetate (ACDASAMe) were synthesized and characterized by spectroscopic methods and in the case of the nickel complex, X-ray single-crystal diffraction. The ligand exhibits the (N, S) coordination mode on interacting with the metal centers. The X-ray structure of the nickel(II) complex reveals a NiN₂S₂ distorted square planar coordination geometry with the ligands showing a cis configuration. There is no interaction between the –CH₂COOMe moieties of the ligand and the metal center, however intermolecular hydrogen bonds through the carbonyl group leads to the building of dimeric associations.