Magnetic and spectral characterisation of some copper(II) chloropropionates with 1-phenyl-2,3-dimethyl-5-pyrazolone

The magnetic susceptibilities in the temperature range 77–290 K of powdered samples of Cu(ClCH₂CH₂COO)₂ A, Cu(CH₃CHClCOO)₂ A and Cu(CH₃CCl₂COO)₂ A, where A is 1-phenyl-2,3-dimethyl-5-pyrazolone, are reported. The data show that an antiferro- magnetic interaction is present with a susceptibility maximum at 262, 245 and 205 K, respectively. The data are compared to the structurally and magnetically related compound, copper(II) acetate monohydrate and are discussed in terms of the Bleaney-Bowers model. Several correlations between the magnetic and spectral data as well as the acidity of the respective acids are discussed.     

Extraction of thorium(IV) as perchlorate and chloroacetate complexes with 1-phenyl-2,3-dimethyl-5-pyrazolone (antipyrine)

Summary Thorium was extracted quantitatively with the neutral ligand 1-phenyl-2,3-dimethyl-5-pyrazolone (Apy) in the presence of perchlorate (ClO₄^-) and di/trichloroacetates (DCA/TCA) at pH 2.5 into an organic solvent. Optimization of experimental parameters like pH, equilibration time, solvents, reactant concentrations, best suited conditions for back extraction, interference due to the presence of different anions and cations and effect of metal ion concentration were studied. The composition of the complexes has been established using log-log plots and are represented as [Th(Apy)₂(ClO₄)₄], [Th(Apy)₂(TCA)₄], [Th(Apy)(H₂O)(DCA)₄]. The respective conditional stability constants of the effectively extracted complexes have also been calculated as 9.4±0.03 and 10.4±0.04, respectively . The method has been extended for the separation of thorium from a number of cations in binary and multicomponent mixtures. The method is simple, rapid, selective and has a good reproducibility (±0.5%).     

Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3-phenyl-4-(p-methoxy- phenylazo)-5-pyrazolone

Mn(II), Co(II), Ni(II) and Cu(II) chelates with3-phenyl-4-(p-methoxyphenylazo)-5-pyrazolone have been synthesized and were characterized by elemental and thermal analyses as well as by IR, UV-VIS, ¹HNMR, conductometric and magnetic measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration, the second denotes the removal of the coordinated water molecules. The final decomposition products were found to be the respective metal oxides. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) 1:1, tetrahedral for Ni(II) 1:1and 2:3; square planar for Cu(II) 1:1 and 2:3; the complexes with no coordinated water molecules (2:3) Co(II) and Mn(II) complexes are tetrahedral. This revised version was published online in August 2006 with corrections to the Cover Date.     

Extractive separation of uranium(VI) as perchlorate/chloroacetate complexes with 1-phenyl-2,3 dimethyl-5-pyrazolone and its applications

The extraction of U(VI) with 1-phenyl 2,3 dimethyl-5-pyrazolone, at a pH of 2.5, in the presence of common anions, like perchlorate and tri-, di-, and monochloroacetates has been investigated. The optimum experimental conditions have been evaluated by studying various parameters such as pH, equilibration period, reagent concentration, metal concentration, and solvents. Effect of diverse anions and cations on the extraction has also been studied. The extracted species, determined by log D - log R plots are represented as, [UO₂(Apy)₄(ClO₄)₂], [UO₂(Apy)₂(TCA)₂], [UO₂(Apy)₂(DCA)₂], [UO₂(Apy)(H₂O)(MCA)₂]. The conditional stability constants of the quantitatively extracted complexes are calculated. The proposed method allows the selective separation of uranium(VI) from multicomponent mixtures and geological matrices and is also applied for the separation and chemical characterization of impurities at trace and ultratrace levels.     

Synthesis,characterization and antibacterial activity of some new complexes of Cu(II), Ni(II), VO(II), Mn(II) with Schiff base derived from 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one

Coordination compounds of Cu(II), VO(II), Ni(II), and Mn(II) with the Schiff base obtained through the condensation of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one with 3-formyl-6-methyl-chromone were synthesized. The characterization of the newly formed compounds was done by ¹H NMR, UV–Vis, IR, ESR spectroscopy, elemental analysis and molar electric conductibility. The crystal structure of 1-phenyl-2,3-dimethyl-4-(N-3-formyl-6-methyl-chromone)-3-pyrazolin-5-one (HL) has been determined by X-ray diffraction studies, as well as the one of its copper(II) complex [CuL(OAc)]·CH₃OH which contains an anionic ligand and an acetate in the coordination sphere of the metal. The single crystal X-ray structure for (HL) was analyzed for its various weak H-bonding and dimeric association.     

Co(II), Ni(II) and Cu(II) complexes of 1,4-di-(1-hydroxyimino-2-phenyl-2-oxo-ethylamino)benzene

The ligand has been prepared from ω-chloroisonitrosoacetophenone and 1,4-phenylenediamine in the presence of NaHCO₃. The ligand have a C=O group and an –NH–R group adjacent to the oxime group. The Ni(II), Cu(II) and Co(II) complexes of the synthesized ligand were prepared and their structures were identified using FTIR, UV-Vis spectral data, elemental analysis, thermal analysis and magnetic moment measurements. The metal-ligand ratios were found to be 3:2. The ligands were found to coordinate to the metal ions via the oxime nitrogen, oxime oxygen, one of the carbonyl group and amide nitrogen atoms. Thermal analyses data reveals that the water in the complexes was found to be non-coordinated to the metal ions. In the trinuclear structures, the metals have the tetrahedral environments.     

Copper(II) complexes with ligands derived from 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one: synthesis and biological activity

The synthesis of Cu(II) complexes derived from Schiff base ligands obtained by the condensation of 2-hydroxybenzaldehyde or terephtalic aldehyde with 4-amino-antipyrine (4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) is presented. The newly prepared compounds were characterized by( 1)H-NMR, UV-VIS, IR and ESR spectroscopy. The determination of the antimicrobial activity of the ligands and of the complexes was carried out on samples of Escherichia coli, Klebsiella pneumoniae, Acinetobacter boumanii, Pseudomonas aeruginosa, Staphylococcus aureus and Candida sp. The qualitative and quantitative antimicrobial activity test results proved that all the prepared complexes are very active, especially against samples of Ps. aeruginosa, A. Boumanii, E. coli and S. aureus.     

Anionic lanthanide complexes with 3-methyl-4-formyl-1-phenyl-5-pyrazolone

The coordination compounds Na[LnL₄] · 2H₂O and [NBu₄][LnL₄] (Ln = Nd, Sm, Eu, Tb; HL is 3-methyl-4-formyl-1-phenyl-5-pyrazolone) have been synthesized and studied by IR spectroscopy and thermogravimetry. According to X-ray diffraction data, the coordination polyhedra of lanthanides are shaped as square antiprisms and formed by the oxygen atoms of four deprotonated moieties of the enol form of 4-formyl-5-pyrazolone. In the complex Na[EuL₄] · 2H₂O, sodium cations are bonded to the two nitrogen atoms of pyrazole heterocycles, combining discrete complex anions into two interpenetrating three-dimensional frameworks. Polycrystalline samples of neodymium(III), samarium(III), and terbium(III) complexes manifest intense luminescence in the spectral regions that are typical for them.     

铽与1-苯基-3-甲基-4-酰代吡唑啉-5-酮的三元配合物的合成、表征与荧光性能

合成了铽与1-苯基-3-甲基-4-异丁酰基吡唑啉-5-酮(HPMIBP)、1-苯基-3-甲基-4-苯甲酰基吡唑啉-5-酮(HPMBP)的四个三元配合物Tb(PMIBP)3.2H2O(A1), Tb(PMIBP)3.bpy(A2), Tb(PMBP)3.2H2O(B1)和Tb(PMBP)3.bpy(B2)(bpy=2, 2'-联吡啶)。用元素分析确定了它们的组成, 并用紫外-可见光谱、红外光谱、差热-热重谱对其进行了表征。研究了它们在固态和溶液中的荧光光谱, 并用频域法测定了它们在溶液中的荧光寿命, 结果表明A1和A2的荧光强度比相应的B1和B2强三个数量级, A2与A1或B2与B1相比, 荧光强度也有一定程度的增强,并且不同溶剂对其荧光强度和荧光寿命都有较大的影响。     

Spectroscopic analysis of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitro-phenyl) acetonitrile

The optimized geometry and vibrational frequencies of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitro-phenyl) acetonitrile (DOPNA) were obtained by ab initio DFT/B3LYP level with complete relaxation in the potential energy surface using 6-31G and 6-311G basis sets. The Fourier-transform infrared (FT-IR) spectrum of DOPNA has been recorded in the region 4000-400 cm(-1). The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR spectrum. The calculated frequencies are in comparable agreement with the experimental frequencies. The calculated energy span between the HOMO and the LUMO of DOPNA is 2.94 and 2.87eV by B3LYP/6-31G and B3LYP/6-311G, respectively.     

Solvent extraction of calcium(II) and strontium(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of calcium and strontium from aqueous solution with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (C_n) in MIBK and benzyl alcohol has been studied. In the extraction of Sr with 4-acyl derivatives-MIBK systems, the pH_1/2 values change with increasing the length of acyl chain in the derivatives. The reagent C₃ is more suitable than the other reagents for the separation of Ca and Sr, using MIBK as solvent.     

Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

Studies on extraction of manganese(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Mn(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA) in MIBK has been studied. Mn(II) is extracted as MnA(2). The extraction constant for each 4-acyl compound was calculated. The effect of temperature on the extraction of Mn(II) has also been investigated.     

Syntheses,characterization and crystal structures of mixed-ligand Cu(II), Ni(II) and Mn(II) complexes of N-(1-phenyl-3-methyl-4-propenylidene-5-pyrazolone)-salicylidene hydrazide containing ethanol or pyridine as a co-ligand

Five new mixed-ligand complexes [CuL(EtOH)] (1), [NiL(EtOH)₃] (2), [Mn₂L₂(μ₂-EtOH)₂(EtOH)₂] (3), [CuL(Py)] · MeOH (4) and [NiL(Py)₃] (5) (L²⁻ = N-(1-phenyl-3-methyl-4-propenylidene-5-pyrazolone)-salicylidene hydrazide anion, Py = pyridine) have been synthesized and characterized by elemental analyses, IR spectra, thermal analyses and single crystal X-ray diffraction. The crystallographic structural analyses of these complexes reveal that the ligand (H₂L) itself undergoes isomerization from the keto form to the enol form in the reaction, then loses two protons and acts as a double negatively charged tridentate chelating agent coordinated to the metal ion in the solution. The final results show that when a co-ligand was present in the synthetic reaction, other coordination sites around the metal ions Cu²⁺ and Ni²⁺ were completed either by the ethanol or pyridine molecules under the common solvent reaction or solvothermal syntheses conditions, respectively. In the case of the Mn²⁺ ion, it was still coordinated with the solvent molecules regardless of whether it was synthesized under the common solvent reaction or solvothermal syntheses with pyridine. The reason for this difference might be attributed to the fact that the coordination modes and bonding effect of the co-ligand with the metal ions are different, the final complexes tend to form the most stable compound.