Chemical and antifungal properties of the copper(II) complexes of 2-formylpyridine4 N-methyl-,4 N-dimethyl,4 N-diethyl and4 N-dipropylthiosemicarbazones

Summary Two series of copper(II) complexes. [Cu(HL)X₂] and [Cu(L)Cl], where HL is a 2-formylpyridine⁴ N-substituted thiosemicarbazone, L is an anion formed by loss of the²N hydrogen and X=Cl or Br, have been prepared and spectrally characterised. Their growth inhibition ofAspergillus niger andPaecilomyces variotii has been measured and compared with analogous complexes formed from 2-acetylpyridine thiosemicarbazones.     

Structural and spectral studies of di-2-pyridyl ketone 3-piperidyl- and 3-hexamethyleneiminylthiosemicarbazone and their cobalt(II), nickel(II) and copper(II) complexes

Cobalt(II), nickel(II) and copper(II) complexes of di-2-pyridyl ketone 3-piperidyl- and 3-hexamethyleneiminyl-thiosemicarbazones (HDPypip and HDPyhexim, respectively) have been prepared and characterized by physical and spectral methods. Use of 1:2 thiosemicarbazone-to-metal chloride molar ratios in the preparation of the complexes has produced both mononuclear and polynuclear species for the three metal ions. Crystal structures of the HDPypip, HDPyhexim and [Ni(DPyhexim)Cl] have been determined and aid the assignments of the i.r., n.m.r., u.v.–vis. n.i.r. and e.s.r. spectra for the various complexes.     

Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 6. The chemical and antifungal properties of 2-acetylpyridine4 N-diethyl- and4 N-dipropylthiosemicarbazones and their copper(II) complexes

Summary Complexes of stoichiometry [CuLX] where X=Cl, Br and L=2-acetylpyridine⁴ N-diethyl- and⁴ N-dipropylthiosemicarbazone, HL4DE and HL4DP, respectively, have substantially more activity againstAspergillus niger andPaecilomyces variotii than the uncomplexed thiosemicarbazones. Spectral data (i.e., i.r., u.v.vis., and e.s.r) of the complexes are presented along with thermodynamic data for the thiosemicarbazones.     

Copper(II) complexes of N,N-dimethyl-2-picolinamine N-oxide

Cu(II) complexes have been prepared with N,N-dimethyl-2-picolinamine N-oxide (DMA) employing the tetrafluoroborate, nitrate, chloride and bromide salts. Complexes having 1:2 and 1:1 metal ion to ligand ratios have been isolated. Characterization has been accomplished by IR, electronic and ESR spectral measurements of the solid state. Significant changes occurred when spectral measurements of acetonitrile solutions of the various solids were attempted indicating alteration of the Cu(II) bonding occurs. Thermal data on the solids are included.     

Physico-chemical properties of the copper(II)-poly-4-vinylpyridine complexes

Water-soluble Cu(II) complexes of poly-4-vinylpyridine, partially quaternized by methyl bromide or dimethylsulphate (PP, Mt) and of the analogue (4-ethylpyridine) were studied by physicochemical technique such as visible spectrophotometry, viscosity, speed sedimentation and EPR spectroscopy. Peculiarities of the complex formation reaction were observed for the polymer compared to the analogue. The predominant formation of tetrapyridinate-Cu(II) species [(CuL₄)]²⁴ was found to take place in aqueous solution for PP, Mt with degree of quaternization (β) 20,24,37,49,57,65 per cent over a wide range of P_YJ Cu(II) molar ratios. In addition, not all the free polymer pyridine residues are capable of forming [Cu L4 ]² complexes even though there is a large excess of Cu(II) ions. The maximum value of the pyridine fraction forming [Cu L₄ ]²¹ in PP_YMt-20, 24, 37, 49 (obtained by spectroscopic titration) was found to be 45–50 per cent. Addition of Cu(NO₃)₂ to the aqueous polymer solution causes strong reduction of specific viscosity and increase of sedimentation coefficient from - 1 S to - 6 S. These data lend to the suggestion of the existence of macromolecular associates bound by Cu(II) ions and approximate estimation of their average molecular weight. It was shown also that Bjerrum's procedure cannot be used to account for the polymer stability constants. The differences between complex formation for polymer pyridine and monomer pyridine seem to be due to the high local pyridine concentration in the coil of the macromolecule and the hydration effects of the polymer chain on the characteristics of the pyridine residues.     

Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 8. The chemical and antifungal properties of the nickel(II) complexes of 2-acetylpyridine4 N-diethyl- and4 N-dipropylthiosemicarbazones

Summary Nickel(II) complexes of 2-acetylpyridine⁴ N-diethyl- and⁴ N-dipropylthiosemicarbazone show less activity againstAspercallus niger than the free thiosemicarbazones. However, againstPaecilomyces variotii the nickel(II) complexes possess comparable activity at high concentrations and are more active at lower concentrations. Spectral and thermal information about the nickel(II) complexes, which coordinate the anionic thiosemicarbazone ligands in a tridentate manner, is included.     

Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 9. The chemical and antifungal properties of the iron(III) and cobalt(II,III) complexes of 2-acetylpyridine4 N-diethyl-and4 N-diopropylthiosemicarbazones

Summary ⁴ N-diethyl- and⁴ N-dipropylthiosemicarbazones of 2-acetylpyridine coordinate to Fe^III, Co^III and Co^II centres as tridentate NNS ligands. Spectral and physical data indicates that the size of the⁴ N-substituents can influence the stereochemistry and stoichiometry of the complexes, which show minimal ability to inhibit fungal growth and are considerably less active than the related copper(II) and nickel(II) complexes.     

Unusual redox and chemical properties of N4-substituted pyridoxal thiosemicarbazone copper(II) complexes: their preparation,properties and reactivities

Summary New copper(II) complexes with pyridoxal N⁴-methylthiosemicarbazone (H₂Methsa), N⁴-ethylthiosemicarbazone (H₂Etthsa) and N⁴-phenylthiosemicarbazone (H₂Phthsa) have been prepared and characterized by analytical, magnetic, spectral, e.s.r. and electrochemical methods. All the compounds exhibit normal magnetic moments at room temperature. The variable temperature magnetic moments, however, show the presence of very weak intramolecular antiferromagnetic interaction (–2J = ca. 30cm^-1) between the copper(II) centres in the complexes. The e.s.r. spectra at 77 K in DMSO indicate the presence of a mixture of monomers and dimers consistent with the dissociation of the complexes. Electrochemical studies in non-aqueous solvents show that the complexes undergo a quasi-reversible one electron facile reduction at markedly low negative potentials versus saturated calomel electrode (s.c.e.).     

Transition metal ion complexes of tiosemicarbazones derived from 2-acetylpyridine. Part 10. A comparison of the chemical and antifungal properties of the copper(II) complexes of 2-acetylpyridine 3-pyrrolidinyl-, 3-piperidinyl-, 3-hexamethyleneiminyl- and 3-azabicyclo[3,2,2]-nonylthiosemicarbazones

Summary Copper(II) complexes of the 3-pyrrolidinylthiosemicarbazones of 2-acetylpyridine and 2-acetylpyridineN-oxide have been prepared and their physical and spectral properties determined. Growth inhibition ofAspergillus niger, Paecilomyces variotii, Penicillium rubrum, andAspergillus terreus by thiosemicarbazones and their copper(II) complexes has been measured. These results are compared to 2-acetylpyridine 3-azacyclothiosemicarbazone ligand complexes.     

Magnetic properties of new copper(II) and [copper(II)]3-manganese(II) complexes of [14]N4 macrocyclic oxamides

Four new complexes of [14]N4 macrocyclic oxamides, namely [CuL1], [CuL2], [(CuL1)3Mn](ClO4)3 and [(CuL2)3 Mn](ClO4)3 [L1 and L2 are the dianions of 2,3-dioxo-5,6: 3,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene (H2L1) and 2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclo-tetradeca-7,11-diene (H2L2), respectively], have been prepared and characterized. The observed magnetic susceptibilities of the [(CuL1)3Mn] (ClO4)3 complex over the ca. 2–300 K range have been fitted to theoretical equations based on the Heisenberg spin Hamiltonian =–2JMn(Cu1+ Cu2+Cu3) and molecular field approximation. The results indicated that both the intramolecular and intermolecular magnetic interactions are antiferromagnetic with JCuMn= –19.8cm–1 and zJ=–1.41cm–1.     

The structure,magnetic and spectral properties of 4-acetylpyridine N-oxide complexes of copper(II) propionates

The synthesis and characterization of CuX₂L; (X = CH₃CH₂COO^?, ClCH₂CH₂COO^?, CH₃CHClCOO^? or CH₃CCl₂COO^?; and L = 4-acetylpyridine N-oxide) is reported. The characterization of these compounds was based on electronic, infrared and EPR spectra, as well as magnetic measurements over the temperature range. Several correlations between the spectral and magnetic data as well as pK_a values of the respective acids were found and discussed. On the basis of spectral and magnetic data the structures of the compounds are discussed.     

Synthesis,crystal structures and properties of two copper(II) 2-aminomethylbenzimidazole complexes

Two new Cu^II complexes, [Cu(Hambi)₂(ClO₄)₂] and [Cu(Hambi)₂(dca)₂] (Hambi = 2-aminomethylbenzimidazole) have been prepared and characterized by X-ray diffraction, electronic paramagnetic resonance (e.p.r.) and i.r. analyses. Both complexes exhibit an elongated octahedral coordination environment with two Hambi ligands situated at the equatorial positions in a trans fashion [Cu—N bond distances range from 1.940(9) to 2.031(9) Å]. In the second complex, a new coordination mode, in which dicyanamide coordinates to copper(II) as a monodentate ligand with the amide nitrogen atom, was observed.     

Electrochemical studies of transition metal complexes of 2-acetyl-pyridine thiosemicarbazones. Part 2. Correlations with spectral and antifungal properties of copper(II) complexes of 2-acetylpyridine 3-azacyclothiosemicarbazones

The electrochemical behaviour of a series of copper(II) complexes of 2-acetylpyridine 3-azacyclothiosemicarbazones is reported. The complexes undergo a quasireversible one electron reduction in the range −0.400 to −0.450 Vversus Ag/AgCl, attributable to the copper(II)/-copper(I) redox couple. The electrochemical, as well as spectral characteristics of these complexes, can be correlated with their antifungal activity againstAspergillus niger, Paecilomyces variotti, Penicillum rubrum andAspergillus terreus.     

X-ray diffraction, magnetochemical, and quantum chemical study of the structure and properties of binuclear copper(II) complexes

The binuclear chelates of copper(II) based on the tridentate azomethine ligands were synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), and magnetic measurements. The quantum-chemical study of the structure and calculation of magnetic properties of the obtained metal-chelates was performed using the density functional theory with the broken symmetry technique. The performed magnetochemical studies in the temperature range 2?C300 K suggest the existence of antiferromagnetic exchange interaction in all obtained complexes. The parameters of the exchange interaction ?2J > 260 cm^?1 were determined experimentally for all compounds, the experimental data is in a good agreement with the results of quantum-chemical calculations.     

Synthesis,characterization, and DNA-binding properties of copper(II), cobalt(II), and nickel(II) complexes with salicylaldehyde 2-phenylquinoline-4-carboylhydrazone

Salicylaldehyde 2-phenylquinoline-4-carboylhydrazone (H₂L), and its novel copper(II), cobalt(II), and nickel(II) complexes MHL · Cl · nH₂O [M=Cu n = 3 (1), M=Co n = 2 (2), M=Ni n = 3.5 (3)] have been synthesized and characterized by elemental analysis, molar conductivity, spectroscopic, and thermal analysis. The interaction of these complexes with calf thymus DNA was investigated by UV absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and viscosity measurements. The results suggest that these complexes bind to DNA via an intercalation binding mode and their affinity to DNA follows the order of 3 > 1> 2. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,properties, and crystal structures of mononuclear nickel(II) and copper(II) complexes with 2-oximino-3-thiosemicarbazone-2,3-butanedione

The tridentate ligand 2-Oximino-3-thiosemicarbazone-2,3-butanedione (Hotsb) reacts with MCl₂ (M = Ni²⁺ or Cu²⁺) to give rise to the mononuclear complexes [Ni(Hotsb)₂]Cl₂ · H₂O (1) and [Cu(Hotsb)Cl₂] · H₂O (2). These complexes have been characterized by X-ray crystallography, spectroscopy, and cyclic voltammetry. The nickel(II) ion in (1) is in a six-coordinate octahedral environment being bonded to the two protonated tridentate ligands which occupy mer positions. The copper(II) ion in (2) is in a five-coordinate square-pyramidal geometry, in which the basal plane is made up the two nitrogens, sulfur, and chloride atom, while the other chloride atom is coordinated at the axial position. The cyclic voltammogram of the complexes displays two one-electron waves corresponding to M^II/M^III and M^II/M^I processes. The electronic as well as infrared spectral properties of the title complexes are reported and discussed.     

The spectrochemical properties of bis(amino hydroxamato)copper(II) complexes

The d-d absorption spectra of CuL₂, where L = glycinehydroxamic acid (Glyha), l-α-alaninehydroxamic acid (Alaha), l-α-leucinehydroxamic acid (Leuha), l-histidinehydroxamic acid (Hisha) and sarcosinehydroxamic acid (Sarha), in aqueous solutions have been treated by the Angular Overlap Model (AOM) in C_2h symmetry. Low symmetry splittings of absorption bands of the measured spectra were found by Gaussian analysis. The ligand field parameters were estimated by the Powell optimize algorithm.     

Synthesis,structural characterization and anticancer properties of p-cymene Ru(II) complexes with 2-(N-methyl-1H-1,2,4-triazol-3-yl)pyridines

Transition Metal Chemistry - The structures of new p-cymene Ru(II) complexes with 2-(1-methyl-1H-1,2,4-triazol-3-yl)pyridine and 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine were established based on...     

Four-coordinate nickel(II) and copper(II) complexes of 7-amino-4-methyl-5-aza-3-heptene-2-one

Summary The condensation of acetylacetone with ethylenediamine yields 7-amino-4-methyl-5-aza-3-heptene-2-one (AEH). This terdentate (N₂O) Schiff base forms various types of ternary complexes, depending on the nature of the second ligand. Examples of five- and six-coordination have been previously reported. The present paper points to the possibility of preparing a less common type of complex,i.e. [M^II(AE)Py]⁺ (M=Ni or Cu) in which the use of a monodentate ligand (pyridine) favours a square planar geometry.