Interaction Of Nickel Research Articles

The Interaction of Nickel (II) Ion with Ethylene Diamine (en) Chelate Using Ethaline (Ionic Liquid) as a Solvent

For this experiment, this is the first time using 1 choline chloride (ChCl): 2 ethylene glycol (EG)based liquid (ethaline) to study the interaction between Ni (II) with ethylene diamine. Two of the optical methods for analyzing spectrophotometric measurements (continuous variations and molar ratio methods) have been utilized for determination of, the stoichiometry and whenever possible, the stability constants of the chelates formed. Job`s method was necessary to determine whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the maximum wavelength and for meaningful conclusions the wavelengths were carefully chosen. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also investigated. The stability constants, K1, K2and K3 for the nickel (II) chelates were calculated by both optical methods, though reliable, and are comparable to literature values.

Thermodynamic modeling of the reaction of simultaneous interaction of nickel (II), cobalt (II) and iron (III) oxides with carbon

This paper considers thermodynamic modeling of electric smelting of Allarechenskoye deposit dumps for nickel, cobalt, and iron extraction. Thermochemical transformations in the reaction of interaction of carbon with oxides of nickel (II), cobalt (II) and iron (III) are considered. The investigations of thermochemical transformations of the chemical-phase composition of the system were carried out using the software complex “Astra-4” developed by a team of scientists at the Bauman Moscow State Technical University. Thermochemical transformations and chemical-phase composition of the system as a function of T (temperature) and P (pressure) were studied. In particular, the temperature was in the range from 973K to 1773K and the pressure range was taken from 0.001 MPa to 0.1 MPa. According to the results, it was found that iron in the system transitions to condensed iron, with the degree of transition (αFe) from 29.0% at T = 1173K to 99.1% at 1773K, the degree of transitions of nickel to condensed nickel is 100% before T = 1273K, and with an increase in temperature from 1273K to 1773K decreases to 99,98%; the transition of cobalt to the gas phase is distributed similarly to nickel.

Nickel(II), copper(II) and zinc(II) complexes with an N-pendent dimethyl derivative of an octamethyl macrocyclic ligand: synthesis, characterization and antimicrobial studies

Interaction of CH3I with L (3,10-C-meso-Me8[14]diene) in the ratio of 4:1 in ethanolic solution at room temperature yielded N-pendent dimethyl derivative [(L-2H)(–CH3)2] denoted by LZ. Interaction of nickel(II) acetate tetrahydrate with LZ and subsequent addition of NaClO4·6H2O produced square planar orange-yellow product, [NiLZ](ClO4)2. The reaction of copper(II) perchlorate hexahydrate with LZ afforded four coordinated square planar red [CuLZ](ClO4)2. However, on the reaction of zinc(II) nitrate hexahydrate with LZ furnished white six coordinated two distereoisomeric complexes [ZnLZα(NO3)2] and [ZnLZβ(NO3)2]. Axial addition reactions on four coordinated square planar [NiLZ](ClO4)2 with KX (X= SCN, NO3, Cl, Br or I) and NaNO2 resulted in six coordinated octahedral and square pyramidal axial addition products, such as [NiLZ(NCS)2], [NiLZ(NO3)(ClO4)], [NiLZCl(ClO4)], [NiLZBr2], [NiLZI2] and [NiLZ(NO2)](ClO4), respectively. However axial substitution reactions on [ZnLZα(NO3)2] with KY (Y= SCN, Cl or Br) and NaNO2 produced six coordinated octahedral axial substitution products [ZnLZα(NCS)2], [ZnLZαCl2], [ZnLZαBr2] and [ZnLZα(NO2)2]. Similarly, the axial substitution reactions on [ZnLZβ(NO3)2] with KI and NaClO4.6H2O resulted in six coordinated octahedral axial substitution products [ZnLZβI2] and [ZnLZβ(H2O)2](ClO4)2, respectively. The compounds have been characterized by analytical, spectroscopic, magnetochemical and conductivity data. The antimicrobial activities of the new ligand and its complexes have been tested against different micro pathogens. Nickel(II), copper(II) and zinc(II) complexes with an N-pendent dimethyl derivative ligand LZ of an octamethyl tetraazmacrocyclic ligand were prepared. The compounds were characterized by different analytical and spectroscopic methods. Antibacterial and antifungal activities of these compounds against some bacteria and fungi were also investigated.

Copper(II) and nickel(II) complexes of an N-pendent bis-(cyanoethyl) derivative of an isomeric hexamethyl tetraazamarocyclic ligand: Synthesis, characterization, electrolytic behavior and antimicrobial studies

Hexamethyl derivative salt of the fourteen membered tetraazamacrocycle, Me6[14]diene.2HClO4 (L.2HClO4) has been synthesized by the condensation of ethylenediamine with acetone in presence of quantitative amount of perchloric acid. This diene ligand salt on reduction with NaBH4 followed by extraction with CHCl3 at pH above 12 resulted in a mixture of isomeric ligands, Me6[14]anes which were separated by fractional crystallization from xylene and designated by ‘tet-a’ and ‘tet-b’. Interaction of ‘tet-b’ with excess of acrylonitrile yielded an N-pendent derivative ‘tet-bx’ in which two cyanoethyl groups were attached on less crowded two trans-N atoms. Interactions of nickel(II) acetate tetrahydrate and copper(II) perchlorate hexahydrate with ‘tet-bx’ followed by subsequent addition of NaClO4·6H2O and HClO4 in case of nickel(II) produced square planar orange [Ni(‘tet-bx’)](ClO4)2 and six coordinated octahedral reddish purple [Cu(‘tet-bx’)(ClO4)2] complex respectively. The axial addition reactions on [Ni(‘tet-bx’)](ClO4)2 with NCS, NO3, NO2, Cl, Br and I afforded different colored six coordinated octahedral axial addition products: violet [Ni(‘tet-bx’)(NCS)2]; violet [Ni(‘tet-bx’)(NO3)(ClO4)]; green [Ni(‘tet-bx’)(NO2)(H2O)](ClO4); brown [Ni(‘tet-bx’)(ClO4)Cl]; brown [Ni(‘tet-bx’)(H2O)Br](ClO4) and pink [Ni(‘tet-bx’)(ClO4)I] respectively. All compounds have been characterized by different analytical and spectroscopic parameters. The antimicrobial activities of the concerned ligand and its complexes have been investigated against different bacteria and fungi.

Core-excited resonances initiated by unusually low energy electrons observed in dissociative electron attachment to Ni(II) (bis)acetylacetonate.

Dissociative electron attachment is a mechanism found in a large area of research and modern applications. This process is initiated by a resonant capture of a scattered electron to form a transitory anion via the shape or the core-excited resonance that usually lies at energies above the former (i.e., >3 eV). By studying experimentally and theoretically the interaction of nickel(II) (bis)acetylacetonate, Ni(II)(acac)2, with low energy electrons, we show that core-excited resonances are responsible for the molecular dissociation at unusually low electron energies, i.e., below 3 eV. These findings may contribute to a better description of the collision of low energy electrons with large molecular systems.

SORPTION OF NICKEL (II) IONS BY CHELATING RESIN WITH IMINODIACETATE FUNCTIONALITY

The regularities of sorption of nickel (II) ions from a monocomponent system on macroporous weakly acidic cationite Lewatit MonoPlus TP 207 were studied. Sorption isotherms were obtained. It is shown that the extraction process can be fairly reliably described by Langmuir and Freundlich equations. The static exchange capacity (SEC) of the resin was determined. The SEC dependencies at temperatures of 305 and 328 K during the sorption process were revealed. Integral kinetic curves were obtained. It is defined that the equilibrium concentration of nickel (II) ions is reached about 13 times faster with temperature increase from 305 to 328 K. The experimental data were processed using equations that take into account the influence of external, internal diffusion, "sorbent-sorbate" and "sorbate-sorbate" chemical interactions. It was found that the main limiting stage of sorption of nickel (II) ions is the internal diffusion. The values of external and internal diffusion rate constants at the indicated temperatures were determined. The kinetic curves were processed by pseudo first and pseudo second order models, which satisfactorily describe the experimental data. According to transition-state theory the thermodynamic characteristics of the activation process (activation energy, entropy, enthalpy, and Gibbs free energy) were calculated. Relatively low activation energy indicates the decisive contribution of diffusion in the process of sorption of nickel (II) ions. Positive entropy is the evidence of nickel hydration shells destruction during the sorption process. Positive enthalpy proves an endothermic nature of interaction of nickel (II) ions and ionogenic groups. Negative Gibbs free energy witnesses to spontaneous course of the reaction in the forward direction. For known values of stability constants the contents of nickel ionic forms and SEC’s were calculated in terms of pH value. Nickel extraction from solution increases with the appearance of singly-charged NiOH+ ions in the pH range from 8 to 9.

C[sbnd]H⋯Ni and C[sbnd]H⋯π(chelate) interactions in nickel(II) complexes involving functionalized dithiocarbamates and triphenylphosphine

New bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1–3) and (N-benzyl-N-substituted benzyldithiocarbamato-S,S′)(isothiocyanato-N)- (triphenylphosphane)nickel(II) (4–6) [where substituted benzyl = 2-HOC6H4CH2 (1,4), 3-HOC6H4CH2 (2,5), 4-FC6H4CH2 (3,6)] were synthesized and characterized using IR, electronic, and NMR (1H and 13C) spectra. X-ray structural analysis of homoleptic complex (1) and heteroleptic complexes (5 and 6) confirmed the presence of four coordinated nickel in a distorted square planar arrangement with NiS4 and NiS2PN chromophores, respectively. The νC–S stretching vibrations are observed around 990 cm−1 without any splitting supporting the bidentate coordination of the dithiocarbamate ligand. Electronic spectral studies of all the complexes (1–6) indicate that the geometry of the nickel atom is probably square planar. NMR spectra of all homoleptic and heteroleptic complexes (1–6) reveal a weak signal associated with the backbone carbon (N13CS2) in the region 204.0–210.0 ppm with a weak intensity characteristic of the quaternary carbon signals. The greater trans influence of triphenylphosphine in complexes 5 and 6 is supported by the long NiS distance compared to other NiS distance which is opposite to the NCS− ligand. In the structure of complex 5, C–H⋯π(chelate) interactions results in polymeric chain. Both structures show intramolecular Ni⋯H interactions but that on 6 is the strongest. C–H⋯π interactions are also found in 1, 5 and 6. Hirshfeld surface analysis and the associated 2D fingerprint plots of 1, 5 and 6 have been studied to evaluate intermolecular interactions. The molecular geometries of complexes 1, 5 and 6 have been optimized by abinitio HF method using LANL2DZ program.

Crystal structure, theoretical and experimental electronic structure and DNA/BSA protein interactions of nickel(II) N2O2 tetradentate Schiff base complexes

Nickel(II) allyl arm Schiff base complexes ([NiL1] and [NiL2]) were synthesized and characterized by elemental analysis and ESI-MS, FT-IR, UV–Vis and 1H NMR spectral techniques. The structure of [NiL1] and [NiL2] were analyzed by single crystal X-ray crystallography reveal nickel complexes have slightly distorted square planar geometry around the metal ions. DFT calculations for [NiL1] and [NiL2] in gas phase were performed using SDD basis set for nickel atom and 6-311G(d,p) basis set for the remaining atoms and also at PW91/TZ2P/ZORA level. The electronic transitions of the complexes in acetonitrile were studied by TD-DFT calculations. The energy decomposition analysis was performed to understand the nature of bonding between Ni(II) and Schiff bases (H2L1 and H2L2) suggests that more covalent nature of bonding is in metal complexes. Hypochromism in absorption spectra, emission intensity decrease in EB-DNA complex and DNA viscosity increase by the addition of increasing concentration of the metal complex indicate intercalative mode of binding of the complex with DNA. The binding constants calculated are of the order of 105M−1. The BSA protein binding behavior with [NiL1] and [NiL2] were investigated using absorption and fluorescence titration experiments show alteration in protein’s microenvironment. Also, molecular docking studies were performed to understand the DNA-complex interactions.

Investigation on biomolecular interactions of nickel(II) complexes with monoanionic bidentate ligands

Reactions of monoanionic bidentate ligands 5-methylsalicylaldehyde (5-msal), 5-bromosalicylaldehyde (5-brsal), 5-nitrosalicylaldehyde (5-nsal) and 2-hydroxy-1-naphthaldehyde (2-hnap) with nickel perchlorate hexahydrate produced nickel(II) complexes 1–4, respectively. Single crystal X-ray analyses of complexes 1 and 2 confirmed bidentate mode of the ligands with O˄O coordination to give square planar geometry around nickel atoms. Complexes 1–4 showed one quasi-reversible redox peak at cathodic region (−0.67 to −0.80 V) and one redox peak at anodic region (+1.08 to +1.44 V) assignable to the Ni(II)/Ni(I) and Ni(II)/Ni(III) redox couples, respectively. The complexes exhibited good bovine serum albumin (BSA) binding abilities with a maximum binding constant of 1.96 × 105 M−1. The binding of complexes with calf thymus DNA (ctDNA) showed that the binding affinity is consistent with an increase in steric bulk of the ligands. The nuclease activity of the complexes showed efficient oxidative cleavage in the presence of hydrogen peroxide as an oxidizing agent. The complexes showed higher zone of inhibition when screened for antimicrobial activity against bacteria and human pathogenic fungi.

Nickel-macrocycle interaction in nickel(II) porphyrins and porphyrazines bearing alkylthio β-substituents: A combined DFT and XPS study

An electronic structure analysis of two nickel(II) tetrapyrrole complexes bearing β-alkylthio substituents, NiOMTP and NiOETPz, has been carried out through a combination of high-resolution XPS experiments and DFT calculations. The Ni 2p XPS spectra show a 0.5 eV shift to higher energy of the Ni 2p[Formula: see text] and Ni 2p[Formula: see text] binding energies on going from the porphyrin to the porphyrazine complex. This shift, which is well-reproduced by relativistic spin-orbit ZORA calculations, is indicative of a depletion of electron density on the central metal. Such a depletion of electron density is related to the macrocycle-induced changes in the metal-ligand interactions. In the porphyrazine complex both the ligand to metal [Formula: see text] donation and the metal to ligand [Formula: see text]-back donation increase. The latter increases slightly more than the former, however, leading to a decrease of electron density on the central metal.

Intermolecular interaction of nickel (ii) phthalocyanine tetrasulfonic acid tetrasodium salt with bovine serum albumin: A multi-technique study

ABSTRACTThe interaction of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt with bovine serum albumin (BSA) has been investigated by combination of fluorescence, UV-vis absorption, Fourier transform infrared (FT-IR), and circular dichorism (CD) spectroscopies as well as through molecular docking. Fluorescence quenching and absorption spectra were investigated as a mean for estimating the binding parameters. Analysis of fluorescence quenching data at different temperatures was performed in order to specify the thermodynamics parameters for interactions of phthalocyanine complex with BSA. According to experimental data it was suggested that phthalocyanine had a significant binding affinity to BSA and the process was entropy driven. Based on the results of molecular docking it was indicated that the main active binding site for this phthalocyanine complex is site I in subdomain IIA of BSA. The results provide useful information for understanding the binding mechanism of anticancer drug-albumin and gives insight into the biological activity and metabolism of the drug in blood.

Interactions of nickel(II) ions in protic ionic liquids comprising N-hexyl(or N-2-ethtylhexyl)ethylenediamines

The interactions of nickel(II) ions in a protic ionic liquid (PIL) comprising monoprotic N-alkyl (alkyl=hexyl or 2-ethylhexyl)–ethylenediaminium ions (HHexen+ or HEthexen+, respectively) combined with bis(trifluoromethanesulfonyl)amide (Tf2N−) or trifluoroacetate (TFA−) ions were investigated using visible (VIS) electronic and extended X-ray absorption fine structure (EXAFS) spectroscopy. These were compared to the analogous nickel(II) complexes in molecular solvents, and copper(II) ion in the same PIL systems. A complete extraction of nickel(II) and copper(II) ions from the aqueous phase was achieved by using the above mentioned PILs with the Tf2N− counter anion. Absorption spectra were used to explore the interaction mode of the nickel(II) ions with the chelating diamine PIL by the addition of nickel(II) salts to the PIL. This demonstrated a dominant formation of the tris(alkyl-en) complex at lower nickel(II) concentrations and changes of the complex to a cis-aniono bis(alkyl-en) complex with the addition of the nickel(II) salts. The ethyl-branch in the cationic unit of the PIL was observed to have a larger effect on the solubility of the copper(II) salts than that of the nickel(II) salts. The EXAFS spectra analysis of the nickel(II) ions in the PILs gives the significant information on the fine structure around the nickel(II) ion coordinated by hexylethylenediamine (Hexen) in the PILs.

Polarographic Interaction of Nickel (II) with Ammonium Piperidine-1-Carbodithioate: Application to Environmental Samples

This paper describes the interaction of nickel (II) with ammonium piperidine-1-carbodithioate (APC) using Direct Current (DC) polarography (DCP) & differential pulse polarography (DPP) at the Dropping Mercury Electrode (DME) in NH4Cl-NH4OH buffer medium at pH 6.0. The polarograms shows a predominant peak for nickel (II)-APC at -1.30 V vs SCE, indicating the production of catalytic hydrogen wave (CHW) due to electrostatic interactions between APC and nickel (II). The interactions were characterized with UV-visible spectrophotometer, FT-IR and cyclic voltammetric techniques. The developed method was applied successfully to determine the nickel (II) levels in leafy vegetables and biological samples with acceptable recoveries.

Polarographic Interaction of Nickel (II) with Ammonium Piperidine-1-Carbodithioate: Application to Environmental Samples

Polarographic Interaction of Nickel (II) with Ammonium Piperidine-1-Carbodithioate: Application to Environmental Samples

Agostic Interactions in Nickel(II) Complexes: Trans Influence of Ancillary Ligands on the Strength of the Bond

The selectivity of transition-metal-catalyzed alkyl cross-coupling is significantly affected by agostic interactions. We report a systematic computational study of how ligand trans influence affects the strength of β-agostic interactions in Ni(II)–ethyl complexes selected to model cross-coupling intermediates. The roles of π back-donation and in-plane π coupling are highlighted. Calculations with carbene ligands illustrate the relevance of these ideas for ligand design.

Ni(II) complexes with non-steroidal anti-inflammatory drug diclofenac: Structure and interaction with DNA and albumins

The interaction of nickel(II) with the non-steroidal anti-inflammatory drug sodium diclofenac (Nadicl) in the presence of the N,N′-donor heterocyclic ligands 2,2′-dipyridylketone oxime (Hpko), 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) leads to the formation of mononuclear Ni(II) complexes. The crystal structure of [Ni(dicl)(Hdicl)(Hpko)2](dicl)·CH3OH·0.6H2O (1·CH3OH·0.6H2O) has been determined by X-ray crystallography. The interaction of the complexes with human or bovine serum albumins has been studied by fluorescence spectroscopy revealing their good binding affinity to the albumins with high binding constant values. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that the complexes can bind to CT DNA with [Ni(dicl)(Hdicl)(Hpko)2](dicl) exhibiting the highest binding constant to CT DNA. Complex 1 can bind to CT DNA via intercalation as concluded by studying its cyclic voltammograms in the presence of CT DNA solution and by DNA solution viscosity measurements, while for complexes [Ni(dicl)2(bipy)] (2) and [Ni(dicl)2(phen)] (3) a non-classic intercalative mode has been concluded. Competitive studies of the complexes with ethidium bromide (EB) have shown their moderate to significant ability to displace the DNA-bound EB suggesting a competition with EB.

Nickel(II) and Cobalt(II) 3‐Hydroxy‐4‐pyridinone Complexes: Synthesis, Characterization and Speciation Studies in Aqueous Solution

AbstractThe interaction of nickel(II) and cobalt(II) with a set of 3‐hydroxy‐4‐pyridinone ligands (Hmpp, Hmepp, Hetpp, Hempp, Hdepp and Hdmpp) was investigated in aqueous solution. The family of chelators under study is pharmaceutically relevant in the treatment of iron‐overloaded patients and it is foreseen to be of use in occupational health situations associated with accumulation of nickel and cobalt such as nasal/pulmonary and skin hazards and allergies. Ligand dissociation constants and stability constants for the cobalt(II) and nickel(II) complexes have been determined by potentiometric methods allowing the establishment of the corresponding speciation plots as a function of pH. The values of the stability constants are consistent with the Irving–Williams series and indicate the formation of stable ML2 complexes which were isolated and characterized. Following the trend observed for 3‐hydroxy‐4‐pyridinone ligands the solids were obtained as hydrates whose composition was characterized as [ML2(H2O)2]·xH2O complexes. DFT calculations allowed geometry optimization and provided information about bond lengths and angles.

Potentiometric Study on Complexation of Divalent Transition Metal Ions with Amino Acids and Adenosine 5′-Triphosphate

Potentiometric equilibrium measurements have been performed at 25 °C and in an I = 0.10 M KCl ionic medium for the interaction of nickel(II), copper(II), and zinc(II) with adenosine 5′-triphosphate (ATP) and dicarboxylic amino acids (aa): aspartic acid (Asp) and glutamic acid (Glu). The formation of 1:1 and 1:2 binary and 1:1:1 ternary complexes was inferred from the potentiometric titration curves. It was deduced that adenosine 5′-triphosphate acts as a primary ligand in the ternary complexes involving the dicarboxylic amino acids. The complexation model for systems of adenosine 5′-triphosphate (ATP) and the dicarboxylic amino acids with nickel(II), copper(II), and zinc(II) have been established by the “BEST” software from the potentiometric data. Values of Δ log K (log βMAB − (log βMA + log βMB)) showed that the ternary complexes are less stable than the binary ones, suggesting that no interaction occurred between the ligands in the ternary complexes. The order of the values of the stability constants of all the ternary complexes was M(II)ATP(Asp) > M(II)ATP(Glu), and the same sequence was found in the binary complexes of metal ions with the amino acids. With respect to the metal ions, the stability constants of binary and ternary complexes decrease in the following order: copper(II) > nickel(II) > zinc(II).

Crystal structures and magnetic interactions in nickel(II) dibridged complexes formed by both phenolate oxygen-azide, or methanlate groups

Tridentate Schiff base ligands L1 and L2, derived from the condensation of 2-hydroxy-3-methoxybenzaldehyde (L) with 2-aminoethanol or 2-aminobutan-1-ol, react with nickel chloride, azide, or thiocyanate to give rise to two dinuclear complexes of formulas [Ni2(L)(L1)2N3]·H2O (1), [Ni2(L2)3(μ1,1-N3)]·2H2O (2), and one tretranuclear complex [Ni2(L2)2(NCS)]2(C2H5OH)2 (3), where L1 = HOCH2CH(C2H5)NCHC6H3(O−)(OCH3) and L2 = HO(CH2)2NCHC6H3(O−)(OCH3). We have characterized these complexes by analytical, crystal structures, and variable temperature magnetic susceptibility measurements. The magnetic properties of the complexes are studied by magnetic susceptibility (χM) vs. temperature measurements. The χM T vs. T plots reveal that compounds 1, 2 and 3 are ferromagnetically coupled. Crystal of two dimers and one tetranuclear nickel (II) complexes were determined. Two dimers are azide/phenolate double bridged, and the tetranuclear is Ni4O4 cubane complex. And magnetic properties show that these compounds are ferromagnetically coupled.

Binding of nickel(II) tetrakis(dimethylpyrazolium-4-yl)porphyrin to poly(dG-dC)2 and poly(dA-dT)2

The interaction of nickel(II) complex of cationic porphyrins bearing five-membered rings, meso-tetrakis(1,2-dimethylpyrazolium-4-yl)porphyrinatonickel(II) (NiPzP) , with synthetic polynucleotides poly(dG-dC)2 and poly(dA-dT)2 has been characterized by viscometric, visible absorption, CD and MCD spectroscopic, and melting temperature measurements. The nickel(II) complex NiPzP is intercalated into poly(dG-dC)2 but outside bound to the major groove of poly(dA-dT)2. The binding constants of NiPzP to poly(dG-dC)2 and poly(dA-dT)2 are in the order of 106 M-1 and comparable to those of other reported cationic metalloporphyrins. The binding process of NiPzP to poly(dG-dC)2 and poly(dA-dT)2 is endothermic and entropically driven.