951 resultados para Affinity ligands
Resumo:
The synthesis of dithiocarbamate ligands based on a pyrrole framework is reported. These ligands self-assemble with zinc(II), nickel(II) and copper(II) to afford neutral, dinuclear metallomacrocycles and trinuclear metallocryptands. The assembled metallo compounds have been characterised by a range of techniques, including H-1 NMR, UV-vis spectroscopy, elemental analysis, mass spectrometry and X-ray crystallography. Some preliminary anion binding studies have also been conducted, using electronic spectroscopy and electrochemistry. The nickel macrocycles showed some affinity for acetate, whereas the copper cryptand showed affinity for benzoate anions. The copper cryptand also exhibited a significant electrochemical response to a range of anions.
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Extended-chain complexes containing multiple transition metal centres linked by conjugated mu-cyanodiazenido(1-) ligands [N= N-C N]-have been obtained by reaction of trans-[BrW(dppe)(2)(N2CN)], 1, [dppe = 1,2-bis(diphenylphosphino) ethane] with dirhodium(II) tetra-acetate, bis(benzonitrile) palladium(II) dichloride, and bis(aqua) M(II) bis(hexa. uoroacetylacetonate) (M = Mn, Ni, Cu, Zn): stronger Lewis acids such as tetrakis(acetonitrile) palladium(II) tetra. uoroborate and boron trifl. uoride promote hydrolysis of complex 1, leading to the isolation of a novel carbamoylhydrazido(2-) complex, trans-[BrW(dppe) 2(N2HC=ONH2)](+)[BF4](-).
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Two linear, trinuclear mixed-valence complexes, [Co-II{(mu-L-1)(mu-OAc)Co-III (OAc)}(2)] (1) and [Co-II(mu-L-2) (mu-OAc)Co-III(OAc)}(2)] (2) and two mononuclear Con' complexes [Co-III{L-3)(OAc)] (3), and [Co-III {L-4}(OAc)] (4) were prepared and the molecular structures of 1, 2 and 4 elucidated on the basis of X-ray crystallography [OAc = Acetate ion, H2L1 = H(2)Salen 1,6-bis(2-hydroxyphenyl)-2,5-diazahexa-1,5-diene, H2L2 H2Me2-Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene, H2L3 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta1,6-diene, H2L4 = H(2)Me(2)Salpn = 2,8-bis(2-hydroxyphenyl)3,7-diazanona-2,7-dienel. In complexes I and 2, the acetate groups show both monodentate and bridging bidentate coordination modes, whereas chelating bidentate acetate is present in 4. The terminal (CoN2O4)-N-III centres in 1 and 2 exhibit uniform facial arrangements of both non-bridged N2O and bridging O-3 donor sets and the Co-II centre is coordinated to six (four phenoxo and two acetato) oxygen atoms of the bridging ligands. The effective magnetic moment at room temperature corresponds to the presence of high-spin Coll in both 1 and 2. The complexes 1 and 2 are thus Co-III(S = 0)Co-II(S = 3/2)-Co-II(S = 0) trimers. Complexes 3 and 4 are monomeric and diamagnetic containing low-spin Co-III(S = 0) with chelating tetradentate Schiff base and bidentate acetate. Calculations based on DFT rationalise the formation of trinuclear or monomiclear complexes. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
Resumo:
Four new copper(II) complexes, [((CuLN3)-N-1)(2)](ClO4)(2) (1), [(CuL2 N-3)(2)](ClO4)(2) (2), [CuL3(N-3)ClO4)](n) (3) and [CuL4(mu-1,1-N-3)(mu-1,3-N-3)(ClO4)](n) (4) where L-1 = N-1-pyridin-2-yl-methylene-propane-1,3-diamine, L-2 = N-1-(1-pyridin-2-yl-ethylidene)propane-1,3-diamine, L-3 =N-1-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine and L-4=N-1-(1-pyridin-2-yl-ethylidene)propane-1,2-diamine are four tridentate N,N,N donor Schiff base ligands, have been derived and structurally characterized by X-ray crystallography. Compounds 1 and 2 consist of double basal-apical end-on (EO) azide bridged dinuclear Cu-II complexes with square-pyramidal geometry. In complex 3 the square planar mononuclear [CuL3 (N-3)] units are linked by weakly coordinated perchlorate ions in the axial positions of Cu-II to form a one-dimensional chain. Two such chains are connected by hydrogen bonds involving perchlorate ions and azide groups. Compound 4 consists of 1-D chains in which the Cu-II ions with a square-pyramidal geometry are alternately bridged by single EO and end-to-end (EE) azido ligands, both adopting a basal-apical disposition. Variable temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K have been performed. The results reveal that complexes 1 and 2 are antiferromagnetically coupled through azido bridges (J= -12.18 +/- 0.09 and -4.43 +/- 0.1 cm(-1) for 1 and 2, respectively). Complex 3 shows two different magnetic interactions through the two kinds of hydrogen bonds; one is antiferromagnetic (J(1) = - 9.69 +/- 0.03 cm(-1)) and the other is ferromagnetic (J(2) = 1.00 +/- 0.01 cm(-1)). From a magnetic point of view complex 4 is a ferromagnetic dinuclear complex (J= 1.91 +/- 0.01 cm(-1)) coupled through the EO bridge only. The coupling through the EE bridge is practically nil as the N(azido)-Cu-II (axial) distance (2.643 angstrom) is too long. (C) 2006 Elsevier Ltd. All rights reserved.
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Background: MHC Class I molecules present antigenic peptides to cytotoxic T cells, which forms an integral part of the adaptive immune response. Peptides are bound within a groove formed by the MHC heavy chain. Previous approaches to MHC Class I-peptide binding prediction have largely concentrated on the peptide anchor residues located at the P2 and C-terminus positions. Results: A large dataset comprising MHC-peptide structural complexes was created by remodelling pre-determined x-ray crystallographic structures. Static energetic analysis, following energy minimisation, was performed on the dataset in order to characterise interactions between bound peptides and the MHC Class I molecule, partitioning the interactions within the groove into van der Waals, electrostatic and total non-bonded energy contributions. Conclusion: The QSAR techniques of Genetic Function Approximation (GFA) and Genetic Partial Least Squares (G/PLS) algorithms were used to identify key interactions between the two molecules by comparing the calculated energy values with experimentally-determined BL50 data. Although the peptide termini binding interactions help ensure the stability of the MHC Class I-peptide complex, the central region of the peptide is also important in defining the specificity of the interaction. As thermodynamic studies indicate that peptide association and dissociation may be driven entropically, it may be necessary to incorporate entropic contributions into future calculations.
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Two sets of nickel(11) complexes of a series of tetradentate NSNO ligands were synthesized and isolated in their pure form. All these complexes, formulated as [Ni(L)Cl](2) and [Ni(L)(N-3)](2) [HL = pyridylthioazophenols], were characterized using physicochemical and spectroscopic tools. The solid-state structures of two complexes (1a and 2a) were established by X-ray crystallography. The geometry about the nickel ion of the complexes is octahedral and the complexes are dimeric in nature. In 1, two Ni(II) ions are bridged by two Cl- anions while in 2 they are bridged by two azide ions in a mu-1,1-bridging fashion. (C) 2008 Elsevier Ltd. All rights reserved.
Resumo:
Two oxorhenium(V) complexes with bidentate phosphine ligands were synthesized and isolated as [ReOCl3(dppm)] 1 and [ReOCl3(dppp)] 2 [where dppm = 1,1-bis(diphenylphosphino) methane and dppp = 1.3-bis(diphenylphosphino) propanel. Complex 2 was structurally characterized. Both the complexes were used as catalysts in the epoxidation of olefins using NaHCO3 as co-catalyst and H2O2 as terminal oxidant. (c) 2008 Elsevier B.V. All rights reserved.
Resumo:
Complexes have been synthesised with bis(2-pyridine carboxaldehyde) ethylenediimine (1) and bis(2-pyridine carboxaldehyde)propylene-1,3-diimine (2) with all of the available lanthanide trinitrates. Crystal structures were obtained for all but one complex with 1 and for all but one complex with 2. Four distinct structural types were established for 1 but only two for 2, although in all cases the structures contained one ligand bound to the metal in a tetradentate fashion. With 1, the four different structures of the lanthanide(III) nitrate complexes included 11-coordinate [Ln(1)(NO3)(3)(H2O)] for Ln = La; 10 coordinate [Ln(1)(NO3)(3)(H2O)] with one monodentate and two bidentate nitrates for Ln = Ce, then 10-coordinate [Ln(1)(NO3)(3)] for Ln = Pr-Yb with three bidentate nitrates; and 9-coordinate [Ln(1)(NO3)(3)] with one monodentate and two bidentate nitrates for Ln = Lu. On the other hand for 2 only two distinct types of structure are obtained, the first type with Ln = La-Pr and the second type for Ln = Sm-Lu, although all are 10-coordinate with stoichiometry [Ln(2)(NO3)(3)]. The difference between the two types is in the disposition of the ligand relative to the nitrates. With the larger lanthanides La-Pr the ligand is found on one side of the coordination sphere with the three nitrate anions on the other. In these structures, the ligand is folded such that the angle between the two pyridine rings approaches 90degrees, while with the smaller lanthanides Sm-Lu, two nitrates are found on one side of the ligand and one nitrate on the other and the ligand is in an extended conformation such that the two pyridine rings are close to being coplanar. In both series of structures, the Ln-N and Ln-O bond lengths were consistent with the lanthanide contraction though there are significant variations between ostensibly equivalent bonds which are indicative of intramolecular hydrogen bonding and steric crowding in the complexes. (C) 2004 Elsevier B.V. All rights reserved.
Resumo:
The ability of new hydrophobic tridentate ligands based on 2,6-bis(benziinidazol-2-yl)pyridine, 2,6-bis(benzoxazol-2-yl)pyridine and 2,6-bis(benzothiazol-2-yl)pyridine to selectively extract americium(III) from europium(III) was measured. The most promising ligand-2,6-bis(benzoxazol-2-yl)-4-(2-decyl-1-tetradecyloxy)pyridine L-9 was found to give separation factors (SFAm/Eu) of up to 70 when used to extract cations from 0.02-0.10 M HNO3 into TPH in synergy with 2-bromodecanoic acid. Six structures of lanthanide complexes with 2,6-bis(benzoxazol-2-yl)pyridine L-6 were then determined to evaluate the types of species that are likely to be involved in the separation process. Three structural types were observed, namely [LnL(6)(NO3)(3)(H2O)2], 11-coordinate only for La, [LnL(6) (NO3)(3) (CH3CN)], 10-coordinate for Pr, Nd and Eu and [LnL(6) (NO3)(3)(H2O)], L 10-coordinate for Eu and Gd. Quantum Mechanics calculations were carried out on the tridentate ligands to elucidate the conformational preferences of the ligands in the free state and protonated and diprotonated forms and to assess the electronic properties of the ligands for comparison with other terdentate ligands used in lanthanide/actinide separation processes.
Resumo:
The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L-5) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D-Am/D-Eu separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO3. Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO3. In order to investigate the possible nature of the extracted species crystal structures of L-5 and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L-4) were also determined. The structure of L-5 shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L-5 is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L-4. The crystal structure of Yb(L-4)(NO3)(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L-4 and L-5 are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L-1) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L-4 and L-5 is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L-1 evolve from the presence of two adjacent nitrogen atoms in the triazine rings.
Resumo:
Quantitative structure activity relationships (QSARs) have been developed to optimise the choice of nitrogen heterocyclic molecules that can be used to separate the minor actinides such as americium(III) from europium(III) in the aqueous PUREX raffinate of nuclear waste. Experimental data on distribution coefficients and separation factors (SFs) for 47 such ligands have been obtained and show SF values ranging from 0.61 to 100. The ligands were divided into a training set of 36 molecules to develop the QSAR and a test set of 11 molecules to validate the QSAR. Over 1500 molecular descriptors were calculated for each heterocycle and the Genetic Algorithm was used to select the most appropriate for use in multiple regression equations. Equations were developed fitting the separation factors to 6-8 molecular descriptors which gave r(2) values of >0.8 for the training set and values of >0.7 for the test set, thus showing good predictive quality. The descriptors used in the equations were primarily electronic and steric. These equations can be used to predict the separation factors of nitrogen heterocycles not yet synthesised and/or tested and hence obtain the most efficient ligands for lanthanide and actinide separation. (C) 2003 Elsevier B.V. All rights reserved.
Resumo:
Recently the BTBP-family of solvating ligands have been studied for their ability to separate trivalent actinides from lanthanides. Five of the BTBPs were evaluated for their ability to extract nickel(II) from aqueous nitrate media into cyclohexanone. It was shown by both solvent extraction and X-ray diffraction experiments that the BTBPs are capable of forming both 1: 1 and 1:2 complexes with nickel(II). When the BTBP concentration is low the nickel distribution ratio is governed by the formation of the nickel/BTBP complex while at higher BTBP concentrations the partitioning of the nickel complex between the two phases dictates the nickel distribution ratio.
Resumo:
The partitioning of minor trivalent actinides (An) from lanthanides (Ln) is one of the challenges in the chemical treatment of nuclear waste. The optimal ligand to carry out the separation of An(III) and Ln(III) using solvent extraction has to meet several important criteria: high selectivity towards the solute, chemical and radiolytic stability, stripping possibilities and recycling of the organic phase, high separation factors and good distribution ratio, to name just a few of them. A chronological line can be drawn along the development of each extraction ligand family and some milestones are emphasized in this overview. Further developments in organic synthesis of extracting ligands are expected.
Resumo:
Molecular modelling studies have been carried out on two bis(calix[4]diqu(inone) ionophores, each created from two (calix[4]diquinone)arenes bridged at their bottom rims via alkyl chains (CH2)(n), 1: n = 3, 2; n = 4, in order to understand the reported selectivity of these ligands towards different sized metal ions such as Na+, K+, Rb+, and Cs+ in dmso solution. Conformational. analyses have been carried out which show that in the lowest energy conformations of the two macrocycles, the individual calix[4]diquinones exhibit a combination of partial cone, 1,3-alternate and cone conformations. The interactions of these alkali metals with the macrocycles have been studied in the gas phase and in a periodic box of solvent dmso by molecular mechanics and molecular dynamics calculations. Molecular mechanics calculations have been carried out on the mode of entry of the ions into the macrocycles and suggest that this is likely to occur from the side of the central cavity, rather than through the main axis of the calix[4]diquinones. There are energy barriers of ca. 19 kcal mol(-1) for this entry path in the gas phase, but in solution no energy barrier is found. Molecular dynamics simulations show that in both 1 and 2, though particularly in the latter macrocycle, one or two solvent molecules are bonded to the metal throughout the course of the simulation, often to the exclusion, of one or more of the ether oxygen atoms. By contrast the carbonyl oxygen atoms remain bonded to the metal atoms throughout with bond lengths that remain significantly less than those to the ether oxygen atoms. Free energy perturbation studies have been carried out in dmso and indicate that for 1, the selectivity follows the order Rb+ approximate to K+ > Cs+ >> Na+, which is partially in agreement with the experimental results. The energy differences are small and indeed the ratio between stability constants found for Cs+ and K+ complexes is only 0.60, showing that 1 has only a slight preference for K+. For the larger receptor 2, which is better suited to metal complexation, the binding affinity follows the pattern Cs+ >> Rb+ >> K+ >> Na+, with energy differences of 5.75, 2.61, 2.78 kcal mol(-1) which is perfectly consistent with experimental results.
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Two new cadmium (II) complexes [Cd(hmt)(dca)(2)] (n) (1) and [Cd-3(hmt)(2)(SeCN)(6)(H2O)(2)] (n) (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN6 chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe2N3O and CdSe2N4 chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and (SeSe)-Se-... interaction are extended to 2D supramolecular architecture.