Synthesis,structure, spectra and redox chemistry of mono- and dinuclear copper(II) complexes containing pyridyl groups

Copper(II) complexes generalized as Cu₂N₆ and CuN₆ were prepared by using hexadentate ligands, and their spectral and electrochemical behavior was analysed. X-ray analysis of binuclear [Cu₂L²Cl₂]²⁺ reveals that one copper is trigonal bipyramidal and the other is square pyramidal. Electronic spectra used to determine their stereochemistry in solution indicate that dinuclear Cu₂N₆ has two visible bands that correspond to a typical five-coordinate copper(II) environment, whereas only one broad band was obtained for mononuclear CuN₆. When NaN₃ was added to the dinuclear compounds, their UV–visible spectra underwent significant changes and an isosbestic point at 650?nm was observed; however, no such feature was encountered for the mononuclear compounds.     

Synthesis,structures and magnetic properties of copper (II) and cobalt (II) complexes containing pyridyl-substituted nitronyl nitroxide and 3,5-dinitrobenzoate

Four new metal-radical complexes - [Cu(NIT3Py)₂(DTB)₂] 1, [Co(NIT3Py)₂(DTB)₂(CH₃OH)₂] 2, [Cu(NIT4Py)₂(DTB)₂(H₂O)₂] 3, [Co(NIT4Py)₂(DTB)₂(H₂O)₂] 4, (NIT3Py = 2-(3^′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide], NIT4Py = 2-(4^′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide], DTB = 3,5-dinitrobenzoic anion) have been synthesized by using transition metal ions, nitronyl nitroxide radicals as spin carriers, and incorporating 3,5-dinitrobenzoic acid (DTB) as a coligand.     

Synthesis,characterization, and electrochemical study of two new macroacyclic Schiff bases and their copper(II) and zinc(II) complexes

Two new potentially octadentate N₂O₆ Schiff-base ligands 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)phenoxy)phenylimino)methyl)-6-methoxyphenol H₂L¹ and 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)-4-tert-butylphenoxy)phenylimino)methyl)-6-methoxyphenol H₂L² were prepared from the reaction of O-Vaniline with 1,2-bis(2′-aminophenoxy)benzene or 1,2-bis(2′-aminophenoxy)-4-t-butylbenzene, respectively. Reactions of H₂L¹ and H₂L² with copper(II) and zinc(II) salts in methanol in the presence of N(Et)₃ gave neutral [CuL¹]?·?0.5CH₂Cl₂, [CuL²], [ZnL¹]?·?0.5CH₂Cl₂, and [ZnL²] complexes. The complexes were characterized by IR spectra, elemental analysis, magnetic susceptibility, ESI–MS spectra, molar conductance (Λ_m), UV-Vis spectra and, in the case of [ZnL¹]?·?0.5CH₂Cl₂ and [ZnL²], with ¹H- and ¹³C-NMR. The crystal structure of [ZnL¹]?·?0.5CH₂Cl₂ has also been determined showing the metal ion in a highly distorted trigonal bipyramidal geometry. The electrochemical behavior of H₂L² and its Cu(II) complex, [CuL²], was studied and the formation constant of [CuL²] was evaluated using cyclic voltammetry. The logarithm value of formation constant of [CuL²] is 21.9.     

EPR and electronic spectral properties of aryl-substituted bis(dithiophosphato)copper(II) complexes

The spectral properties of bis(diaryl-dithiophosphato)copper(II) complexes, [Cu(S(2)P(OR)(2))(2)], with R = o-cresyl (complex I) and 2,6-dimethylphenyl (complex II) are studied by EPR- and vis spectroscopy. In solid (powder) state both complexes exhibit dark brown colour and are paramagnetic. Room temperature EPR spectra of the complexes dissolved in non-coordinating (C(6)H(5)CH(3), C(5)H(12), C(6)H(14)), acceptor (CHCl(3), CCl(4)) or donor (DMFA, DMSO) solvents have typical features of the chromophore CuS(4). In non-coordinating and acceptor solvents their isotropic EPR parameters are: g(iso)=2.047+/-0.003, (Cu)A(iso) = 7.2+/-0.1 mT and (P)A = 0.95+/-0.1 mT. An absorption band characterizes the vis spectra in these solvents with a maximum at 427 nm, due to a ligand-to-metal charge-transfer transition. One hour after dissolution the absorbance at 427 nm follows Beer's law with molar absorptivity (epsilon) about 11000, which does not change significantly after 24 h staying at room temperature or after 30 min heating at 50 degrees C. Both DMFA and DMSO exhibit specific solute-solvent interaction with the acceptor centre of copper complex yielding an axial adduct, with increased g-factor and decreased (hf)A compared to the initial complex. An additional EPR signal with unresolved hyperfine structure is also detected in DMSO. EPR and vis intensities of both bis(diaryl-dtp)Cu(II) complexes decrease after dissolution in both solvents. Moreover, they are EPR silent in pyridine and do not show any absorption in the vis spectra.     

Synthesis,spectroscopy and thermal analysis of copper(II) hydrazone complexes

The chelating behavior of some hydrazones towards Cu(II) has been investigated. The isolated complexes were characterized by elemental analysis, magnetic moment, spectra (electronic, IR and ms) and thermal measurements. The IR spectra showed that the ligands are deprotonated in the complexes as bidentate, tridentate and binegative tridentate. Protonation constants of the ligands and the stability constants of their Cu(II) complexes were calculated. Square-planar, square-pyramidal, tetrahedral and/or distorted octahedral structures are proposed. The TGA data help to confirm the chemical formula of the complexes and indicated the steps of their thermal degradations.     

Synthesis, X-ray structure and properties of a new nitrite-bound copper(II) complex with 2-(3,5- dimethylpyrazol-1-ylmethyl)pyridine in a CuN4(O) coordination

Synthesis and characterization of a nitrite-bound copper(II) compound [CuL⁴)₂(ONO)]ClO₄ have been achieved (L⁴ = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L⁴ provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the d_x²−y² orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible Cu^II---Cu^I response [cathodic peak potential, E_pc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible Cu^II---Cu^I redox response [ ].     

The structures and cyclic voltammetry of three copper(II) complexes derived from bulky ortho-hydroxy Schiff bases

Three copper(II) complexes derived from bulky ortho-hydroxy Schiff base ligands, (1)-(3), were synthesized and characterized by chemical analysis, UV-Vis, IR, μ_eff and mass spectrometry. The solid state structures of compounds (1)-(3) were determined. The solid state X-ray diffraction studies of these compounds show that the geometry is intermediate between square planar and tetrahedral. Moreover, EPR studies in DMF solution at 77 K suggest that the geometry of these complexes in solution is different from that observed in the solid state by X-ray crystallography. Furthermore, cyclic voltammetry studies performed for (1)-(3), indicate a dependence of the cathodic potentials upon conformational and electronic effects.     

Synthesis,characterization and comparative studies of mono- and dimeric copper(II) complexes containing tripodal ligands

Mono and dimeric bromo-bridged copper(II) complexes of the type [CuBr₂(L)] and [Cu₂Br₂(L)₂](ClO₄)₂ containing nitrogen donor tripodal ligands L = 2,6-bis(pyrazol-1-yl)pyridine (bppy) or 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (dmbppy) have been synthesized. All complexes have been characterized by elemental analysis, IR, ESR and electronic spectra and magnetic susceptibility and cyclic voltammetry measurements.     

Synthesis and characterization of two temperature-dependent copper(II) complexes based on 2,6-dimethylpyridine-3,5-dicarboxylate

Two temperature-dependent Cu(II) compounds, [Cu(mpdaH)₂(H₂O)₄] · 4H₂O (1) and [Cu(mpdaH)₂] _n (2) (H₂mpda = 2,6-dimethylpyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions and characterized by X-ray single crystal diffraction, elemental analysis, thermogravimetric analyses, and IR spectra. The structure at room temperature confirms that 1 is mononuclear with the octahedral coordination geometry. However, on warming to 120°C the same reaction gives 2, in which copper(II) has square planar coordination and is further bridged by mpdaH^? ligands to form extended 2-D layers with parallelogram-like (4,4) topology. Furthermore, in both complexes, through π–π stacking and hydrogen bonding interactions, 3-D supramolecular networks are assembled.     

Manganese(II) complexes with bis(3-halo-2-hydroxy- 5-methylacetophenone)ethylenediamine; structure,characterization and redox behavior

A series of manganese(II) complexes containing tetradentate Schiff-base ligands have been synthesized. The Schiff-base ligands were obtained by condensation of salicylaldehyde, 2-OH acetophenone or 2-OH, 3-X, 5-methyl acetophenone with ethylenediamine (X?=?Cl, Br, I). The complexes have been characterized by elemental analysis, IR, UV-VIS, ESMS, EPR spectroscopy, cyclic voltammetry and thermal analysis. The cyclic voltammograms of the complexes exhibit quasi-reversible behavior. The electrochemical potentials are influenced by the methyl and halogen atoms grafted on the ligand molecules. An EPR spectrum for the polycrystalline sample shows one broad isotopic signal as compared with the six lines for frozen solution in DMF.     

Synthesis and selected reactions of pentakis ( t -octylisocyanide)cobalt(II) complexes

The ligand 1,1,3,3-tetramethylbutylisocyanide, CNCMe₂CH₂CMe₃, i.e. t-octylisocyanide, with Co(ClO₄)₂ · 6H₂O or Co(BF₄)₂ · 6H₂O in ethanol, produces pentakis(alkylisocyanide)cobalt(II) complexes, [Co(CNC₈H₁₇-t)₅](ClO₄)₂ (1) and [Co(CNC₈H₁₇-t)₅](BF₄)₂ · 2.0H₂O (2). These Co(II) complexes undergo reduction/substitution upon reaction with trialkylphosphine ligands to produce [Co(CNC₈H₁₇-t)₃{P(C₄H₉-n)₃}₂]ClO₄ (3), [Co(CNC₈H₁₇-t)₃{P(C₄H₉-n)₃}₂]BF₄ (4), and [Co(CNC₈H₁₇-t)₃{P(C₃H₇-n)₃}₂]ClO₄ (5). Complex 3 is oxidized with AgClO₄ to produce [Co(CNC₈H₁₇-t)₃{P(C₄H₉-n)₃}₂](ClO₄)₂ (6). Complex 1 yields [Co(CNC₈H₁₇-t)₄py₂](ClO₄)₂ (7) upon dissolving in pyridine. Reactions with triarylphosphine and triphenylarsine ligands were unsatisfactory. The chemistry of 1 and 2 is therefore more similar to that of Co(II) complexes with CNCMe₃ than with CNCHMe₂, other alkylisocyanides, or arylisocyanides, but shows some behavior dissimilar to any known Co(II) complexes of alkylisocyanides or arylisocyanides. Infrared and electronic spectra, magnetic susceptibility, molar conductivities, and cyclic voltammetry are reported and compared with known complexes. ¹H, ¹³C, and ³¹P NMR data were also measured for the diamagnetic complexes 3, 4, and 5.     

Synthesis,structure and spectroscopic study of Cu(II) polypyridine complexes with phenylcyanamide derivative ligands

Several new mononuclear copper(II) complexes, [Cu(phen)₂L]PF₆, where phen = 1,10-phenanthroline and L = monoanions of phenylcyanamide (pcyd), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd), 2-dichlorophenylcyanamide (2-Clpcyd) and 4-methylphenylcyanamide (4-Mepcyd), have been prepared and characterized by elemental analysis, UV–Vis, IR and ¹H NMR spectroscopies and cyclic voltammetry. [Cu(phen)₂(2,5-Cl₂pcyd)]PF₆ crystallized with a molecule of acetone with empirical formula of C₃₁H₂₀N₆OF₆Cl₂PCu in a triclinic crystal system and space group P 1 with a = 9.2086(6) Å, b = 13.3117(9) Å, c = 15.5313(10) Å, α = 107.8210(10)°, β = 104.6180(10)°, γ = 104.1670(10)°, V = 1643.21(19) ų and Z = 2. The structure was refined using 7555 Mo-Kα reflections with I > 2σ(I) and R ₁ = 0.0276 and Rw = 0.0692. The results are consistent with a mostly σ bonding interaction between Cu(II) and cyanamide anion. The LMCT band intensity and electrochemical potentials are compared with ruthenium phenylcyanamide analogues.     

Thermal behaviour of hydrated copper(II) complexes

Dehydration steps of aquacopper(II) complexes with homogeneous and heterogeneous coordination sphere are investigated from the view point of structural changes taking place under their heating to the decomposition temperature and during the dehydration. The role of loosening of intra-and intermolecular hydrogen bonds in the decomposition reaction for the structure changes of the remainder, the structural presumptions of the reactants for lower hydrates formation are discussed. Activation parameters of dehydration were found to be the lower, the smaller are the structure differences between the reactants and products. They do not reflect the bond length central atomvolatile ligand, much more the overall structure differences between the starting and resulting compounds. From all data on crystal and molecular structures of dehydrated compounds is the reaction pathway best indicated by anisotropic temperature parameters of donor atoms corrected for the thermal movement of the central atom: the higher these values in the bond direction are, the lower the values of activation energies of dehydration are.     

Synthesis and antimicrobial activities of metal(II) complexes with bis(2,4-diiodo-6-propyliminomethyl-phenol)-pyridine

Seven new mononuclear complexes have been synthesized from 2,4-diiodo-6-propyliminomethyl-phenol in pyridine and Cu(OAc)₂ · H₂O, Ni(OAc)₂ · 4H₂O, Co(OAc)₂ · 4H₂O, Zn(OAc)₂ · 2H₂O, Cd(OAc)₂ · 2H₂O, Mn(OAc)₂ · 4H₂O, and Hg(OAc)₂. The complexes were characterized by UV, IR, ESI-MS, and elemental analyses; bis(2,4-diiodo-6-propyliminomethyl-phenol)-pyridine-copper(II) (1) was characterized by X-ray crystallography. The central metal in each complex is five-coordinate by two nitrogens and two oxygens from two 3,5-diiodosalicylaldehyde Schiff-base ligands and one nitrogen from pyridine. The 3,5-diiodosalicylaldehyde Schiff base is bidentate. All the complexes were assayed for antibacterial (Bacillus subtilis, Staphylococcus aureus, Streptococcus faecalis, Pseudomonas aeruginosa, Escherichia coli, and Enterobacter cloacae) activities by the MTT method. Complex 1 showed the most favorable antimicrobial activity with minimum inhibitory concentrations of 6.25, 3.125, 6.25, 3.125, 6.25, 3.125 µg mL^?1 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli, and E. cloacae, respectively.     

Synthesis,characterization and catalytic activity of halo-methyl-bis(salicylaldehyde)ethylenediamine cobalt(II) complexes

The synthesis, characterization and catalytic activity of a series of tetra-halo-dimethyl salen and di-halo-tetramethyl-salen ligands are reported in this paper: α,α′-dimethyl-Salen (dMeSalen) (L¹); 3,3′,5,5′-tetrachloro-α,α′-dimethyl-Salen, (tCldMeSalen) (L²); 3,3′-dibromo-5,5′-dichloro-α,α′-dimethyl-Salen, (dCldBrdMeSalen) (L³); 3,3′,5,5′-tetrabromo-α,α′-dimethyl-Salen, (tBrdMeSalen) (L⁴); 3,3′,5,5′-tetraiodo-α,α′-dimethyl-salen, (tIdMeSalen) (L⁵); 3,3′-dichloro-5,5′,α,α′-tetramethyl-Salen (dCltMeSalen) (L⁶); 3,3′-dibromo-5,5′,α,α′-tetramethyl-Salen (dBrtMeSalen) (L⁷); and 3,3′-diiodo-5,5′,α,α′-tetramethyl-Salen (dItMeSalen) (L⁸) (Salen = bis(salicylaldehyde)ethylenediamine). Upon reaction with Co(II) ions, these ligands form complexes with square planar geometry that have been characterized by elemental analysis, cyclic voltammetry, UV–Vis, IR and EPR spectroscopies. In the presence of pyridine the obtained Co(II) complexes were found able to bind reversibly O₂, which was shown by EPR spectroscopy and cyclic voltammetry. They were also found able to catalyze the oxidation of 2,6-di-tert-butylphenol (DtBuP) (9) with formation of 2,6-di-tert-butyl-1,4-benzoquinone (DtBuQ) (10) and 2,6,2′,6′-tetra-tert-butyl-1,1′-diphenobenzoquinone (TtBuDQ) (11). These properties are first influenced by the coordination of pyridine in axial position of the Co(II) ion that causes an increase of the electronic density on the cobalt ion and as a consequence a decrease in the E_1/2 value and an increase of the reducing power of the Co(II) complex. It is noteworthy that, under those conditions the complexes also show a remarkable quasi-reversible behaviour. Second, complex properties are also influenced by the substituents (methyl and halogen) grafted on the aromatic ring and on the azomethynic groups. The donating methyl substituent on the azomethynic groups causes a decrease in the E_1/2 value, whereas the halogen substituents on the aromatic rings have two effects: a mesomeric donating effect that tends to lower the redox potential of the complex, and a steric effect that tends to decrease the conjugation of the ligand and then to increase the redox potential of the Co(II) complex. In pyridine, the steric effect predominates, which causes both an increase of the redox potential and a decrease of the selectivity of the oxidation of phenol 9. As a result of all these effects, it then appears that the best catalysts to realize the selective oxidation of 2,6-di-tert-butyl-phenol (9) by O₂ are the Co complexes of ligands bearing CH₃ donating substituents, Co(dMeSalen) 1 (2CH₃ substituents), and Co-di-halo-tetra-methyl-salen complexes 6, 7 and 8 (4CH₃ substituents), in the presence of pyridine.     

Synthesis,spectroscopic characterization,X-ray structure and DFT calculations of five-coordinated chlorocopper(II) complex with bis(3,5-dimethylpyrazol-1-yl)methane

The reaction of copper dichloride dihydrate and bis(3,5-dimethylpyrazol-1-yl)methane affords [Cu{H₂C(3,5-Me₂pz)₂}₂Cl]Cl · 3H₂O. The compound has been studied by IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure of the [Cu{H₂C(3,5-Me₂pz)₂}₂Cl]⁺ cation has been calculated with the density functional theory (DFT) method. The spin-allowed doublet–doublet electronic transitions of [Cu{H₂C(3,5-Me₂pz)₂}₂Cl]⁺ have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis.