13 resultados para Complexes de nickel(II)
em Aston University Research Archive
Resumo:
The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.
Resumo:
The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.
Resumo:
Five manganese complexes in an N 4O 2 donor environment have been prepared. Four of the compounds involve aroyl hydrazone as ligands and manganese is in a +2 oxidation state. The fifth compound was prepared using N,Nprime-o-phenylenebis(salicylideneimine) and imidazole as ligands where manganese is present in +3 oxidation state. X-ray crystal structure of one Mn +2 compound and the Mn +3 compound was determined. The relative stabilities of the Mn +2 and Mn +3 oxidation states were analyzed using the structural data and MO calculations. Manganese(II) complexes of four aroyl hydrazone ligands were prepared and characterized by different physicochemical techniques. The complexes are of the type Mn(L) 2, where L stands for the deprotonated hydrazone ligand. One of the compounds, Mn(pybzhz) 2, was also characterized by single crystal structure determination. In all these complexes, the Mn(II) is in an N 4O 2 donor environment and the Mn(II) center cannot be oxidized either chemically or electrochemically. However, when another ligand Ophsal is used to give the compound [Mn(Ophsal)(imzH) 2]ClO 4, which was also characterized by X-ray crystal structure determination, manganese can easily avail the +3 oxidation state. The relative stabilities of the +2 and +3 oxidation states of manganese were analyzed and it was concluded that the extent of distortion from the perfect octahedral geometry is the main controlling factor in these cases. © 2004 Elsevier B.V. All rights reserved.
Resumo:
Copper(II) complexes of some pyridine-2-carboxamidrazones have been prepared and characterized. The crystal structures of the copper complex cis-[dichloro(N1-2-acetylthiophene-pyridine-2-carboxamidrazone) copper(II)] 8a and one of the free ligands, viz. {(p-chloro-2-thioloxy-benzylidine-pyridine-2-carboxamidrazone)} 6, have been determined. The former shows a highly distorted square planar geometry around copper, with weak intermolecular coordination from the thiophenyl sulfur resulting in a stacking arrangement in the crystal lattice. The in vitro activities of the synthesized compounds against the malarial parasite Plasmodium falciparum are reported for the first time, which clearly shows the advantage of copper complexation and the requirement of four coordinate geometry around copper as some of the key structural features for designing such metal-based antimalarials. © 2003 Elsevier Science B.V. All rights reserved.
Resumo:
Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands Heda3p and Heddadp (Heda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3- propionic acid) have been prepared. An octahedral trans(O) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8HO compound, while Ba[Cu(eddadp)]·8HO is proposed to adopt a trans(O ) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial ß-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.
Resumo:
The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.
Resumo:
A series of manganese(II) [Mn(L)] and manganese(III) [Mn(L)(X)] (X = ClO4, OAc, NCS, N3, Cl, Br and I) complexes have been synthesized from Schiff base ligands N,N′-o- phenylenebis(salicylideneimine)(LH2) and N,N′-o-phenylenebis(5- bromosalicylideneimine)(L′H2) obtained by condensation of salicylaldehyde or 5-Br salicylaldehyde with o-phenylene-diamine. The complexes have been characterized by the combination of IR, UV-Vis spectroscopy, magnetic measurements and electrochemical studies. Three manganese(III) complexes 3 [Mn(L)(ClO4)(H2O)], 5 [Mn(L)(OAc)] and 13 [Mn(L)(NCS)] have been characterized by X-ray crystallography. The X-ray structures show that the manganese(III) is hexa-coordinated in 3, it is penta-coordinated in 13, while in 5 there is an infinite chain where the MnL moieties are connected by acetate ions acting as bridging bidentate ligand. The cyclic voltammograms of all the manganese(III) complexes exhibit two reversible/quasi-reversible/ irreversible responses assignable to Mn(III)/Mn(II) and Mn(IV)/Mn(III) couples. It was observed that the ligand L′H2 containing the 5-bromosal moiety always stabilizes the lower oxidation states compared to the corresponding unsubstituted LH2. Cyclic voltammograms of the manganese(II) complexes (1 and 2) exhibit a quasi-reversible Mn(III)/Mn(II) couple at E1/2 -0.08 V for 1 and 0.054 V for 2. © 2005 Elsevier B.V. All rights reserved.
Resumo:
MHC class II proteins bind oligopeptide fragments derived from proteolysis of pathogen antigens, presenting them at the cell surface for recognition by CD4+ T cells. Human MHC class II alleles are grouped into three loci: HLA-DP, HLA-DQ and HLA-DR. In contrast to HLA-DR and HLA-DQ, HLA-DP proteins have not been studied extensively, as they have been viewed as less important in immune responses than DRs and DQs. However, it is now known that HLA-DP alleles are associated with many autoimmune diseases. Quite recently, the X-ray structure of the HLA-DP2 molecule (DPA*0103, DPB1*0201) in complex with a self-peptide derived from the HLA-DR a-chain has been determined. In the present study, we applied a validated molecular docking protocol to a library of 247 modelled peptide-DP2 complexes, seeking to assess the contribution made by each of the 20 naturally occurred amino acids at each of the nine binding core peptide positions and the four flanking residues (two on both sides).
Resumo:
A multinuclear Fe-Mn-Cr complex with 4-amino-1,2,4-triazole (NH2trz) and oxalate (ox) ligands has been synthesized successfully. The formula of the [Fe(NH2trz)3][ClO4][MnCr(ox)3].4H2O complex has been obtained based on the metal and C, H, N contents. The presence of water molecules, metal-ligand bonding and bridge ligand in the multinuclear complex has been confirmed by its infrared spectrum. The compound crystallizes in the hexagonal system with cell parameters of a = b = 18.695 Å and c = 57.351 Å. The compound shows a gradual spin crossover for iron(II) in the [Fe(NH2trz)3]2+ with transition temperature (T1/2) of 205 K. The antiferromagnetic interaction between Cr(III) and Mn(II) ions in the [MnCr(ox)3]n n- network is observed from the Weiss constant (θ) of –2.3 K.
Resumo:
The effect of brittle coating precracking on the fatigue behavior of a high-activity aluminide-coated single-crystal nickel-base superalloy has been studied using hollow cylindrical specimens at test temperatures of 600 °C, 800 °C, and 1000 °C. Three types of precrack were studied: narrow precracks formed at room temperature, wide precracks formed at room temperature, and narrow precracks formed at elevated temperature. The effect of precracking on fatigue life at 600 °C was found to depend strongly on the type of precrack. No failure was observed for specimens with narrow room-temperature precracks because of crack arrest via an oxidation-induced crack closure mechanism, while the behavior of wide precracks and precracks formed at elevated temperature mirrored the non-precracked behavior. Crack retardation also occurred for narrow room-temperature precracks tested at 800 °C - in this case, fatigue cracks leading to failure initiated in a layer of recrystallized grains on the inside surface of the specimen. A significant reduction in fatigue life at 800 °C relative to non-precracked specimens was observed for wide precracks and elevated temperature precracks. The presence of precracks bypassed the initiation and growth of coating fatigue cracks necessary for failure in non-precracked material. No effect of precracking was observed at 1000 °C.
Resumo:
Two modified Jacobsen-type catalysts were anchored onto an amine functionalised hexagonal mesoporous silica (HMS) using two distinct anchoring procedures: (i) one was anchored directly through the carboxylic acid functionalised diimine bridge fragment of the complex (CAT1) and (ii) the other through the hydroxyl group on the aldehyde fragment of the complex (CAT2), mediated by cyanuric chloride. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, DRIFT, UV-vis, porosimetry and XPS which showed that the complexes were successfully anchored onto the hexagonal mesoporous silica. These materials acted as active heterogeneous catalysts in the epoxidation of styrene, using m-CPBA as oxidant, and α-methylstyrene, using NaOCl as oxidant. Under the latter conditions they acted also as enantioselective heterogeneous catalysts. Furthermore, when compared to the reaction run in homogeneous phase under similar experimental conditions, an increase in asymmetric induction was observed for the heterogenised CAT1, while the opposite effect was observed for the heterogenised CAT2, despite of CAT2 being more enantioselective than CAT1 in homogeneous phase. These results indicate that the covalent attachment of the Jacobsen catalyst through the diimine bridge leads to improved enantiomeric excess (%ee), whereas covalent attachment through one of the aldehyde fragments results in a negative effect in the %ee. Using α-methylstyrene and NaOCl as oxidant, heterogeneous catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier Inc. All rights reserved.
Resumo:
Quercetin is a naturally occurring polyphenol compound present in grapes, red wine, tea, apples and some vegetables. Like other flavonoids, it has been found to have antioxidant activity in studies in vitro, although there is still much debate about the bioavailability of flavonoids in the diet and their in vivo antioxidant activity. In general, it is thought that the antioxidant efficiency of polyphenols increases with increasing hydroxylation of the rings, but there have been few studies of other substitutions. We have prepared several derivatives of quercetin, to test the effect of modification on their antioxidant potential. Sodium salts of quercetin-5-sulfonate and quercetin-5,8-sulfonate, and transition metal complexes of quercetin-5-sulfonate were analysed for their total antioxidant potential using the FRAP assay, and compared to unmodified quercetin. It was found that quercetin-5-sulfonate complexes with Zn, Cu(II), Fe(II) and Mg were all significantly better antioxidants than quercetin, quercetin-5-sulfonate was comparable to quercetin, whereas the sodium salt of quercetin-5,8-sulfonate had a decreased total antioxidant potential. Kinetic studies of the FRAP reaction showed no significant differences between quercitin and any of the derivatives. The reaction of all the quercetins in the FRAP assay was found to be slower to reach completion than ascorbate, and appeared to have biphasic characteristics. These results suggest that transition metal ions may facilitate the transfer of electrons from the polyphenol ring system to the oxidant, while substitution with S03 is electron-withdrawing and destabilizes the ring system. This is important both for understanding the antioxidant ability of flavonoids, and for the design of novel antioxidant compounds. Further work is being carried out to assess the ability of the quercetin complexes to protect cultured cells from oxidative stress.
Resumo:
The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.