Synthesis, structural and corrosion inhibition studies on cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 2-acetylthiophene benzoylhydrazone

Cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 2-acetylthiophene benzoylhydrazone have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, electronic, IR, NMR and ESR spectral techniques. The molecular structures of ligand and its copper(II) complex have been determined by single crystal X-ray diffraction technique. The Cu(II) complex possesses a CuN₂O₂ chromophore with a considerable delocalization of charge. The structure of the complex is stabilized by intermolecular π–π stacking and C–H?π interactions. Hatbh acts as a monobasic bidentate ligand in all the complexes bonding through a deprotonated C–O⁻ and >CN groups. Electronic spectral studies indicate an octahedral geometry for the Ni(II) complex while square planar geometry for the Co(II) and Cu(II) complexes. ESR spectrum of the Cu(II) complex exhibits a square planar geometry in solid and in DMSO solution. The trend g_|| > g_⊥ > 2.0023 indicates the presence of an unpaired electron in the d_x²-y² orbital of Cu(II). The electro-chemical study of Cu(II) complex reveals a metal based reversible redox behavior. The Ni(II) complex shows exothermic multi-step decomposition pattern of the bonded ligand. The ligand and its most of the metal complexes show appreciable corrosion inhibition properties for mild steel in 1 M HCl medium. [Co(atbh)₂] complex exhibited the greatest impact on corrosion inhibition among the other compounds.     

Copper(II) complexes as superoxide dismutase mimics: Synthesis, characterization, crystal structure and bioactivity of copper(II) complexes

Two new copper(II) complexes of the type [Cu(L)X₂), where L = (E)-N-phenyl-2-[phenyl (pyridine-2-yl)methylene]hydrazinecarboxamide X = Cl/Br have been synthesized and characterized by elemental analyses, FAB (fast atomic bombardment) magnetic measurements, electronic absorption, conductivity measurements cyclic voltammetry (CV) and Electron paramagnetic resonance (epr) spectroscopy. The structures of these complexes determined by single crystal X-ray crystallography show a distorted square based pyramidal (DSBP) geometry around copper(II) metal center. The distorted CuN₂OX (X = Cl/Br) basal plane in them is comprised of two nitrogen and one oxygen atoms of the meridionally coordinated ligand and a chloride or bromide ion and axial position is occupied by other halide ion. The epr spectra of these complexes in frozen solutions of DMSO showed a signal at g ca. 2. The trend in g-value (g_|| > g_⊥ > 2.00) suggest that the unpaired electron on copper(II) has d_x²-y² character. Biological activities in terms of superoxide dismutase (SOD) and antimicrobial properties of copper(II) complexes have also been measured. The superoxide dismutase activity reveals that these two complexes catalyze the fast disproportionation of superoxide in DMSO solution.     

Ditopic bis(oxazolines): Synthesis and structural studies of zinc(II), copper(II) and nickel(II) complexes

The synthesis, crystal structures, magnetic and spectroscopic properties of zinc(II), nickel(II) and copper(II) dinuclear complexes 2-4 of a novel dinucleating polyoxazoline ligand 1 are reported. X-ray analysis revealed that the three complexes are centrosymmetric dinuclear species with an overall S shape, the bisoxazoline moieties pointing toward the aromatic core of the molecule. Magnetic susceptibility measurements suggest that there is a very weak exchange interaction between the copper or nickel ions in complexes 3 and 4.     

Bis(isocyclam)dicopper(II) complexes with a linear methylene chain bridge

New binucleating ligands, bis(isocyclam) with a linear methylene chain bridge, n-bicy (n = 2, 3, 4) and their copper(II) complexes, Cu₂(n-bicy)(ClO₄)₄· xH₂O and Cu₂(n-bicy)(NCS)₄·yH₂O have been synthesized. The magnetic moments of these complexes were normal, but the presence of magnetic coupling between copper(II) ions were clearly demonstrated by the hyperfine structure in the ESR spectra.     

Uranyl(VI), copper(II) and nickel(II) complexes derived from a new compartmental ligand

A new heptadentate compartmental ligand has been synthesized by condensation of 3-formylsalicylic acid and 1,5-diamino-3-thiapentane in methanol (H₄L_a). This Schiff base contains an inner N₂SO₂ and an outer O₂O₂ site and gives, by reaction with copper(II), nickel(II) and uranyl(VI) diacetate, mononuclear, homo- and heterobinuclear complexes. In the mononuclear copper and nickel complexes, the metal ion is in the inner N₂SO₂ site, while it is in the outer O₂O₂ for uranyl; a solvent molecule fills the fifth equatorial coordination position in this last complex. The physico-chemical properties of the compounds are discusscd on the basis of infrared, electronic and magnetic data and by comparison with the analogous complexes with the ligand obtained by reaction of 3- formylsalicylic acid and diethylenetriamine (H₄L_b). The mononuclear copper and the heterodinuclear copper-uranyl complexes show anomalously low magnetic moments.     

Novel organic-inorganic molecular assembly: a copper(I) and copper(II) mixed-valent cluster with bromide bridges and paramagnetic ligands

Complex pbt₂Cu₈Br₁₂ [pbt=pyridine-2,6-diylbis(methyleneamino-TEMPO)] was synthesized from CuBr₂ and a new ligand pbt, and characterized by means of X-ray crystal structure analysis and magnetic measurements. The centrosymmetric molecule consists of a Cu₆Br₁₀ cluster sandwiched with two pbt·CuBr complexes. Detailed geometrical analysis and magnetic analysis reveal the presence of four copper(I) and four copper(II) ions in a molecule. Antiferromagnetic couplings observed can be attributed to the intermolecular radical?radical and intramolecular copper(II)?copper(II) interactions.     

Synthesis,physico-chemical studies of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes with some p-substituted acetophenone benzoylhydrazones and their antimicrobial activity

Complexes of the type [M(pabh)(H₂O)Cl], [M(pcbh)(H₂O)Cl] and [M(Hpabh)(H₂O)₂ (SO₄)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest as the ground state. The ligand is bidentate bonding through >C = N ? and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H₂O)₂(SO₄)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H₂O)Cl] and [Ni(Hpabh)(H₂O)₂(SO₄)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand.     

Synthesis, structure and biomimetic properties of Cu(II)-Cu(II) and Cu(II)-Zn(II) binuclear complexes: possible models for the chemistry of Cu-Zn superoxide dismutase

Four imidazolate-bridged binuclear copper(II)-copper(II) and copper(II)-zinc(II) complexes viz., [(Bipy)(2)Cu-Im-Cu(Bipy)(2)](ClO(4))(3).CH(3)OH, [(Phen)(2)Cu-Im-Cu(Phen)(2)](BF(4))(3).2CH(3)OH, [(Bipy)(2)Cu-Im-Zn(Bipy)(2)](BF(4))(3), and [(Phen)(2)Cu-Im-Zn(Phen)(2)](BF(4))(3), (Bipy=2,2'-Bipyridyl, Phen=1-10-Phenanthroline and Im=imidazolate ion) were synthesized as a possible models for superoxide dismutase (SOD). Complex [(Bipy)(2)Cu-Im-Cu(Bipy)(2)](ClO(4))(3).CH(3)OH has been structurally characterized. This complex crystallizes in the triclinic space group P1, with the unit parameters a=8.88(5) A, b=13.79(17) A, c=20.18(18) A, alpha=76.424(8)(o), beta=85.888(6)(o), gamma=82.213(7). The metal-nitrogen bond length from 1.972-2.273 A and the distance Cu-Cu is 5.92 A. The five-coordinate geometry about the copper(II) ion is square pyramidal. Magnetic moment and electron paramagnetic resonance (e.p.r.) spectral measurements of the homobinuclear complexes have shown an antiferromagnetic exchange interaction. From the e.p.r. and UV-Vis spectral measurement studies, these complexes have been found to be stable (pH 8.5-10.5 for 1, 10.5 for 2,3 and 8.5 for 4). These complexes catalyse the dismutation of superoxide radical (O(2)(-)) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase.     

Crystal structures and magnetic properties of tetranuclear copper(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine with a defective double-cubane core

Tetranuclear Cu(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine (H₂L1-H) and its homologues (5-CH₃: H₂L1-Me, 5-Cl: H₂L1-Cl), [Cu(L1-H)]₄ · 3H₂O (1), [Cu(L1-Me)]₄ · 2CH₂Cl₂ (2), and [Cu(L1-Cl)]₄ · 2CH₂Cl₂ (3), have been characterized by X-ray crystal structure analyses and magnetic measurements. The structure analyses revealed that the complexes 1-3 have a defective double-cubane tetra copper(II) core connected by μ₃-alkoxo bridges. The intramolecular Cu?Cu distances are in the range from 5.251(2)-5.256(3) Å for the longest to 3.0518(9)-3.092(2) Å for the shortest. Each Cu(II) ion has a square-pyramidal geometry and the dihedral angles between adjacent Cu(II) basal planes are almost right angles. Magnetic measurements of the present complexes indicate that weak antiferromagnetic interactions (J=−15 to −19 cm⁻¹) between neighboring copper(II) ions are dominant in these tetracopper cores.     

Synthesis,spectral characterization and in vitro biological studies of Co(II), Ni(II) and Cu(II) complexes with 1,2,4-triazole Schiff bases

A series of metal complexes of cobalt(II), nickel(II) and copper(II) have been synthesized with newly derived biologically active ligands. These ligands were synthesized by the condensation of 3-substituted-4-amino-5-hydrazino-1,2,4-triazole and 8-formyl-7-hydroxy-4-methylcoumarin. The probable structure of the complexes has been proposed on the basis of elemental analyses and spectral (IR, Uv-Vis, magnetic, ESR, FAB-mass and thermal studies) data. Electro chemical study of the complexes is also reported. All these complexes are non-electrolytes in DMF and DMSO. All the ligands and their Co(II), Ni(II) and Cu(II) complexes were screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Staphylococcus pyogenes and Pseudomonas aeruginosa) and antifungal (Aspergillus niger, Aspergillus flavus and cladosporium) activities by MIC method. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties.     

Copper(II) complexes with an avian prion N-terminal region and their potential SOD-like activity

Potentiometric and spectroscopic (UV-Vis, CD and EPR) studies were carried out on copper(II) complexes with chicken prion protein N-terminal fragments, Ac-(PHNPGY)₄-NH₂, and the mutated residue, Ac-(PHNPGF)₄-NH₂, to assess the role of tyrosine in the copper coordination. Both thermodynamic and spectroscopic results indicate that chicken prion fragments are not able to bind more than two copper ions and only with the involvement of side chain tyrosine groups. The prevailing complex shows one copper ion bound to four imidazole nitrogen atoms in the 1:1 metal to ligand ratio systems. The superoxide dismutase (SOD)-like activity of copper(II) complexes with the avian peptides and mammal analogue, Ac-(PHGGGWGQ)₄-NH₂, was also investigated by means of Pulse radiolysis. The copper(II) complexes with avian peptides do not display SOD-like activity, while very low activity has been detected for the copper(II) complexes with mammalian tetraoctarepeat.     

N-(2-Pyridyl)acetamide complexes of palladium(II), cobalt(II), nickel(II), and copper(II)

N-(2-Pyridyl)acetamide (aapH) complexes of palladium(II), cobalt(II), nickel(II), and copper(II) have been studied by means of magnetic susceptibilities, and infrared, electronic, and PMR spectra. In the octahedral complexes M(aapH)₂X₂(M = Co, Ni, Cu; X = Cl, Br, NCS, NO₃), bidentate aapH is chelated through the pyridine-N and amid-O atomes, whereas in the square-planar Pd(aapH)₂X₂ (X = Cl, Br) unidentate aapH is coordinated through the pyridine-N atom alone. Under alkaline conditions aapH is deprotonated in the presence of palladium(II) to form Pd(aap)₂·4H₂O, aap being an anionic bidentate ligand and chelating through the pyridine-N and amide-O atoms.     

Spectroscopic,structural and antibacterial properties of copper(II) complexes with bio-relevant 5-methyl-3-formylpyrazole N(4)-benzyl-N(4)-methylthiosemicarbazone

The coordination behaviour of the title ligand, 5-methyl-3-formylpyrazole N(4)-benzyl-N(4)-methylthiosemicarbazone(HMPz4BM), is reported with solid state isolation of copper(II) complexes, [Cu(HMPz4BM)X₂] (X = Cl, Br, NO₃, ClO₄ and BF₄) which have been spectroscopically and structurally characterised. I.r. data for the free ligand and its Cu(II) complexes indicate that HMPz4BM exhibits a neutral NNS tridentate function via the pyrazolyl nitrogen(tertiary), azomethine nitrogen and thione sulphur. Electronic spectral data are suggestive of a square pyramidal environment for the seemingly pentacoordinated Cu(II) species. E.s.r parameters (RT and LNT) of the reported copper(II) complexes are indicative of a dx_x2–y2 ground state for the reported species. Cyclic voltammograms of Cu(II) complexes show a quasireversible Cu^II/Cu^III couple and also an irreversible Cu^II/Cu^I couple. X-ray crystallography of a representative species, [Cu(HMPz4BM)(NO₃)₂] (C2/c, monoclinic ), has unambiguously documented the conjectural findings from i.r. data that coordinating sites of the title ligand are pyrazolyl (tertiary)nitrogen, azomethine nitrogen and the thione sulphur (NNS); and the oxygen of one of the nitrate ions has occupied the basal plane; the fifth coordination position has been occupied by the oxygen of another nitrate ion in a square pyramidal geometry. The antibacterial properties of the ligand and its copper(II) complexes studied on microorganism, Staphylococcus aureus have pointed out that most of the complexes have higher activities than that of the free ligand.     

New acyclic and cyclie Schiff bases derived from 2,6-diformyl-4-chlorophenol and their interaction with uranyl(Vl), copper(II) and nickel(Il) ions

A new heptadentate compartmental ligand has been synthesized by condensation of 3-formylsalicylic acid and 1,5-diamino-3-thiapentane in methanol (H₄L_a). This Schiff base contains an inner N₂SO₂ and an outer O₂O₂ site and gives, by reaction with copper(II), nickel(II) and uranyl(VI) diacetate, mononuclear, homo- and heterobinuclear complexes. In the mononuclear copper and nickel complexes, the metal ion is in the inner N₂SO₂ site, while it is in the outer O₂O₂ for uranyl; a solvent molecule fills the fifth equatorial coordination position in this last complex. The physico-chemical properties of the compounds are discusscd on the basis of infrared, electronic and magnetic data and by comparison with the analogous complexes with the ligand obtained by reaction of 3- formylsalicylic acid and diethylenetriamine (H₄L_b). The mononuclear copper and the heterodinuclear copper-uranyl complexes show anomalously low magnetic moments.     

Synthesis and spectral investigation of manganese(II), cadmium(II) and oxovanadium(IV) complexes with 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone): Crystal structure of manganese(II) and cadmium(II) complexes

The chelating behavior of 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) (H₂dapa) towards manganese(II), cadmium(II) and oxovanadium(IV) ions has been studied by elemental analyses, conductance measurements, magnetic properties and spectral (IR, ¹H NMR, UV-Vis and EPR) studies. The IR spectral studies suggest the pentadentate nature of the ligand with pyridine nitrogen, two azomethine nitrogens and two carbonyl oxygen atoms as the ligating sites. Six coordinate structure for [VO(H₂dapa)]SO₄ · H₂O and seven coordinate structures for [Mn(H₂dapa)(Cl)(H₂O)]Cl · 2H₂O and [Cd(H₂dapa)Cl₂] · H₂O complexes have been proposed. Pentagonal bipyramidal geometry for [Mn(H₂dapa)(Cl)(H₂O)]Cl · 2H₂O and [Cd(H₂dapa)(Cl₂)] · H₂O complexes was confirmed by single crystal analysis. The X-band EPR spectra of the oxovanadium(IV) and manganese(II) complexes in the polycrystalline state at room (300 K) and also at liquid nitrogen temperature (77 K) were recorded and their salient features are reported.     

Mononuclear nickel(II) and copper(II) complexes with Schiff base ligands derived from 2,6-diformyl-4-methylphenol and S-methylisothiosemicarbazones

Four new square-planar Ni(II) and Cu(II) complexes with [N₂O₂] binding system were synthesized by metal-directed condensation of 2,6-diformyl-4-methylphenol with benzoyl or acetylacetone mono-S-methylisothiosemicarbazone. Only mononuclear “one-armed” complexes were obtained as a consequence of the different reactivity of the two carbonyl groups in the hydroxydialdehyde. The complexes were characterized by elemental analysis, EI MS and UV-Vis spectroscopy. The structural assignment was confirmed by X-ray diffraction analysis and NMR spectroscopy, for the Ni(II) complexes, and by ESR spectroscopy and magnetic measurements, for the Cu(II) complexes.     

Dinuclear Ni(II) and Cu(II) complexes with indolecarboxamide ligand: Synthesis, structure and properties

A potential tetradentate indolecarboxamide ligand, H₄L³ is synthesized and investigated for its coordination abilities towards Ni(II) and Cu(II) ions. Two H₄L³ ligands in their tetra-deprotonated form [L³]⁴⁻, were found to coordinate two metal centers resulting in the formation of [Ni₂(L³)₂]⁴⁻ (5) and [Cu₂(L³)₂]⁴⁻ (6) complexes. The crystal structure of 6 displays the formation of a dinuclear structure where two fully deprotonated ligands, [L³]⁴⁻ hold two copper(II) ions together. Even more interesting is the fact that both deprotonated ligands, [L³]⁴⁻ coordinate the copper ions in an identical and symmetrical fashion. The Na⁺ cations present in the complex 6 stitch together the dinuclear units resulting in the formation of a coordination chain polymer. Four sodium ions connect two dinuclear units via interacting with the O_amide groups. Further, Na⁺ cations were found to coordinate several DMF molecules; some of them are terminal and a few are bridging in nature. The solution state structure (determined by the NMR spectral analysis) of the diamagnetic complex 5 also supported the fact that two deprotonated ligands, coordinate two nickel ions in an identical and symmetrical fashion. Absorption spectral studies reveal that the solid-state square-planar geometry is retained in solution and both complexes do not show any tendency to coordinate potential axial ligands. The variable-temperature magnetic measurements and EPR spectra indicate spin-spin exchange between two copper centers in complex 6. The electrochemical results for both complexes show three irreversible oxidative responses that correspond to the oxidation of first and second metal ion followed by the ligand oxidation, respectively.     

Synthesis, crystal structure, cytotoxic activities and DNA-binding properties of new binuclear copper(II) complexes bridged by N,N′-bis(N-hydroxyethylaminoethyl)oxamide

Two new μ-oxamido-bridged binuclear copper(II) complexes with formulae of [Cu₂(heae)(pic)₂] (1) and [Cu₂(heae)(Me₂phen)₂](ClO₄)₂ · H₂O (2), where heae and pic stand for the anion of N,N′-bis(N-hydroxyethylaminoethyl)oxamide and 2,4,6-trinitrophenol, respectively, and Me₂phen represents 2,9-dimethyl-1,10-phenanthroline; have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR and electronic spectra studies. The crystal structures of the two binuclear copper(II) complexes have been determined by X-ray single-crystal diffraction. In both the two binuclear complexes the central two copper(II) atoms are bridged by trans-heae. In complex 1 the coordination environment around each copper(II) atom can be described as a distorted octahedral geometry, while in complex 2 each copper(II) atom displays a square-pyramid stereochemistry. Hydrogen bonding and π-π stacking interactions link the binuclear copper(II) complex 1 or 2 into a 3D infinite network. The cytotoxicities of the two binuclear copper(II) complexes were tested by Sulforhodamine B (SRB) assays against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549. Both of the two binuclear copper(II) complexes exhibit potent cytotoxic effects against SMMC-7721 and A549 cell lines. The interactions of the two binuclear complexes with herring sperm DNA (HS-DNA) are investigated by using absorption and emission spectra and electrochemical techniques and viscometry. The results suggest that both the two binuclear copper(II) complexes interact with HS-DNA in the mode of intercalation with the intrinsic binding constants of 1.73 × 10⁵ M⁻¹ (1) and 1.92 × 10⁶ M⁻¹ (2). The influence of structural variation of the terminal ligands in the binuclear complexes on DNA-binding properties is preliminarily discussed.     

Coordination properties of ethyl bis(pyridin-2-ylmethyl)phosphate ligand with copper and zinc chloride. X-ray crystal structure of Cu(II) complex

A new ethyl bis(pyridin-2-ylmethyl)phosphate (2-bis(pm)Ope) ligand has been synthesized and used for synthesis of copper(II) and zinc(II) complexes of the formula [MCl₂(2-bis(pm)Ope)] [M = Cu(II), Zn(II)]. Despite having the same general formula, Cu(II) and Zn(II) complexes are not isostructural. The Zn(II) complex is four coordinated (MCl₂N₂) forming probably tetrahedral structure whereas the Cu(II) complex of distorted square pyramidal geometry is five coordinated (MCl₂ON₂). The later compound not only coordinates by two nitrogen atoms of pyridine rings but also by the oxygen atom of pyridin-2-ylmethoxyl residue. The compound (2-bis(pm)Ope) has been obtained as the product of diethyl (pyridin-2-ylmethyl)phosphate’s (2-pmOpe) transestrification. The compounds have been identified and characterized by IR, far-IR, ¹H NMR, ³¹P NMR and elemental analyses. The crystal structure of copper(II) complex i.e. [CuCl₂(2-bis(pm)Ope)] has been determined by the X-ray diffraction method. The low temperature magnetic study reveals significant antiferromagnetic interaction between copper centers through the H-bond system.     

Unusual dinuclear copper(II) and nickel(II) complexes of a novel Schiff base deriving from 2-aminoethanol

It is generally accepted that copper(II) complexes involving 2-aminoethanol or a Schiff base deriving from this aminoalcohol display a tetranuclear structure with a Cu₄O₄ ‘cubane’ core. Using a Schiff base obtained by reacting 2′-aminoacetophenone with 2-aminoethanol, we have prepared copper(II) and nickel(II) complexes whose properties are fully consistent with a dinuclear structure. The copper complex is characterized by a low antiferromagnetic interaction.