Potentiometric determination of stability constants of metal complexes with certain amino dicarboxylic acids

A number of new amino dicarboxylic acids were prepared for biological research purposes and their acid dissociation constants measured, as well as the chelate stability constants of their corresponding anions with divalent Mg, Ca and Ni. The amino acids investigated were: N-benzyl (I), N-phenacyl (II), N-(ß-phenoxyethyl) (III), and N-(p-bromoacetanilido) (IV) imino diacetic acids, as well as N-benzyl aspartic acid (dl) (V). The phenoxy-ether oxygen atom in III, in contrast to the ether oxygen atom in N-methoxyethyl-imino diacetic acid, has only very little co-ordination tendency. On the other hand, carbonyl oxygen atoms of keto (II) or amido (IV) groups behave as additional co-ordination sites with some metal ions. The order of stability of the different metal ion complexes with imino diacetic acid derivatives is in agreement with that of many other amino-polycarboxylic acids, showing the anomalous low stability of the Mg chelates and the high stability of the Ca chelates. On the other hand the chelate stability constants of N-benzyl aspartic acid parallel the electronegativities of the metal ions: complexes are formed with Mg ions but not to any measurable extent with Ca. The results are discussed in relation to those previously reported for imino diacetic acid derivatives carrying donor oxygen atoms in their side chains.     

Solution stability constants of complexes of benzohydroxamic acid with some divalent metal ions

The thermodynamic metal-ligand stability constants of the benzohydroxamic acid with divalent metal ions Cu²⁺, Zn²⁺, Ni²⁺, and Mn²⁺ are determined in 50 volume per cent aqueous dioxane media at 35°C following the Bjerrum-Calvin titration technique as applied by Van Uitert et al. to mixed aqueous solvents. Calculations have been made by solving simultaneous equations adapting the procedure as outlined by Goldberg.     

Determination of stability constants of some bivalent metal complexes with thiovioluric and diphenylthiovioluric acids

Stability constants of complexes of some bivalent metal ions, viz, Cu(II), Ni(II), Zn(II), Pb(II) and Mg(II) with thiovioluric and diphenylthiovioluric acid have been determined potentiometrically in 50 and 75% dioxan media, respectively. The order of stability constants for the complexes investigated has been found to be: Mn < Ni < Cu > Zn. The stability of lead complexes has been found to be intermediate between Mn(II) and Ni(II) while magnesium forms the least stable complexes.     

Redox method for the determination of stability constants of some trivalent metal complexes

Stability constants determination of very stable metal complexes using the redox method, based on the equilibrium of Fe (3+)Fe (2+) followed by a couple of platinum/reference electrodes, was undertaken and tested to complexes of some trivalent metal ions with well known polyaminopolycarboxymethylated linear ligands (edta, nta, cdta, dtpa and ttha) and also to some new macrocyclic ligands. SUPERQUAD program was used for the calculations, after adaptation of the experimental data. The method proved to be very useful for Fe(3+) and In(3+) complexes, if no polynuclear complexes are formed or/and if the kinetics of the complexation reaction is not very slow. However, for the Ga(3+) complexes the applicability of this method is very limited and the competition with OH(-) using the displacement reaction which occurs at pH higher than 6 with formation of Ga(OH)(4)(-) seems to give more accurate results. A complete data of stability constants for the case of the complexes of ttha with In(3+) is given.     

The stability constants of some bivalent metal complexes of α-hydroxyisobutyrate and lactate

The stability constants of the lactate and α-hydroxyisobutyrate complexes of Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺ and UO₂²⁺ were determined by potentiometric titration. The average ligand number exceeds 2, indicating the formation of ML⁺, ML₂ and ML₃^- complexes. The existence of ML₃^- complexes was confirmed by electrophoretic experiments; no polynuclear complexes were formed. α-Hydroxyisobutyrate forms stronger complexes than lactate.     

Prediction of chromatographic retention of metal complexes from stability constants measured by ion chromatography

Chromatographia - A theoretical model is used to predict retention times of divalent metal cations in single-column ion chromatography using one or more ligands in the eluent. Stability constants...     

Stability constants of 2-mercaptohistamine metal complexes

Summary Stability constants of 2-mercaptohistamine (2-MH) with a number of transition metal ions were determined by a potentiometric titration method and the coordination mode of (2-MH) metal complexes were thereby characterized. With Mn^II, Fe^ll, Co^II, and Ni^II, coordination occurred through both the imidazole-nitrogen and amino groups, while with Zn^II, Cd^II, Pb^II, and Hg^II, both thiolate and amino groups, contribute to the coordination. in the 2-MH copper complex, polymer formation is suggested on the basis of visible absorption and e.p.r. spectra.     

Determination of stability constants of valinomycin complexes with ammonium and alkali metal ions by capillary affinity electrophoresis

Capillary affinity electrophoresis (CAE) has been employed to investigate quantitatively the interactions of valinomycin, macrocyclic depsipeptide antibiotic ionophore, with univalent cations, ammonium and alkali metal ions, K(+), Cs(+), Na(+), and Li(+), in methanol. The study involved measuring the change in effective electrophoretic mobility of valinomycin while the cation concentrations in the BGE were increased. The corresponding apparent stability (binding) constants of the valinomycin-univalent cation complexes were obtained from the dependence of valinomycin effective mobility on the cation concentration in BGE using a nonlinear regression analysis. The calculated apparent stability constants of the above-mentioned complexes show the substantially higher selectivity of valinomycin for K(+) and Cs(+) ions over Li(+), Na(+), and NH(4)(+) ions. CAE proved to be a suitable method for the investigation of both weak and strong interactions of valinomycin with small ions.     

Spectrophotometric studies,stability constants and thermodynamics for complexes ofo-hydroxyacetophenone isobutyroylhydrazone with some bivalent transition metal ions

Summary The u.v. spectra ofo-hydroxyacetophenone isobutyroylhydrazone (HAIBuH) were investigated in pure organic solvents as well as in Britton Robinson buffer solutions of varyingpH values. The interaction ofHAIBuH with Co(II), Ni(II) and Cu(II) were studied spectrophotometrically. The optimumpH favouring the formation of the highly coloured complexes are 8.5, 8.0 and 7.5 for Co(II), Ni(II) and Cu(II), respectively. The stoichiometries of these complexes were determined and indicated the formation of 1:2 (metal:ligand) complexes of Co(II) and Ni(II) and a 1:1 complex of Cu(II). The dissociation constantspK ^H ofHAIBuH and the overall stability constants log of their complexes were determined at different temperatures (293, 303 and 313 K). The corresponding thermodynamic parameters (G, H and S) in 20% (v/v) ethanol-water mixture were derived and discussed.

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Spektrophotometrische Untersuchungen, Stabilitätskonstanten und Thermodynamik der Komplexe vono-Hydroxyacetophenonisobutyroylhydrazon mit einigen bivalenten Übergangsmetallionen

Zusammenfassung Die UV-Spektren vono-Hydroxyacetophenon-isobutyroylhydrazon (HAIBuH) wurden in reinen organischen Solventien und in Britton-Robinson-Pufferlösungen von verschiedenempH gemessen. Die Wechselwirkung vonHAIBuH mit Co(II), Ni(II) und Cu(II) wurde spektrophotometrisch untersucht. Die optimalenpH-Werte zur maximalen Ausbildung der starkgefärbten Komplexe sind 8.5, 8.0 bzw. 7.5 für Co(II), Ni(II) bzw. Cu(II). Für die Stöchiometrien wurde ein Metall: Ligand-Verhältnis 1:2 für Co(II) und Ni(II) und 1:1 für Cu(II) bestimmt. Die DissoziationskonstantenpK ^H vonHAIBuH und die Gesamtstabilitätskonstanten log der Komplexe wurden bei verschiedenen Temperature bestimmt (293, 303 und 313 K) und die entsprechenden thermodynamischen Parameter (G, H und S) in 20% (v/v) Ethanol-Wasser-Mischung errechnet und diskutiert.

     

An investigation into the determination of stability constants of metal complexes by convolution-deconvolution cyclic voltammetry

A technique is described for calculating stability constants of metal-ligand complexes from convolution-deconvolution voltammetry. Semi-integration of the cyclic voltammetric currents with respect to time allows calculation of E(1 2 ) values in a manner comparable to the use in polarography of the Heyrovsky-Ilkovic equation. The technique described also allows determination of the ratio of the diffusion coefficients of the free and complexed metal ions and provides a second check of the stoichiometry. A reliable route to the metal-complex stability constants by the equations of Lingane and DeFord and Hume is therefore obtained. Advantages of this technique compared with the use of polarography, differential pulse polarography and pH titrations are discussed, with the complexes formed by cadmium with glycine, alanine, valine and aspartic acid as examples.     

Determination of stability constants for alkaline-earth and alkali metal ion complexes of glycine by spectrophotometry

The complex equilibria between alkaline-earth and alkali metal ions with glycine were studied by a spectrophotometric method. The following stability constant (concentration) values valid at 25 degrees and ionic strength 1.0M were found: K(HL) = 10(9.57), K(LiL) = 10(-1.2), K(BaL) = 10(-0.40), K(SrL) = 10(0.14), K(CaL) = 10(0.55), K(MgL) = 10(1.17).     

Radiometric determination of stability constants of mercury species complexes with L-cysteine

Liquid-liquid distribution method has been applied for the determination of the composition and stability constants of mercury species with L-cysteine /H₂L/. In the pH range 2–8, mercury /II/ forms a complex Hg/HL/₂ with very high stability constant /lg ₂ = 40.0/, whereas methylmercury and phenylmercury form complexes CH₃HgHL /lg ₁ = 15.56/ and C₆H₅HgHL /lg ₁ = 16.5/. At pH13, anionic complexes HgL ₂ ^2– /lg ₂ = 42.7/, CH₃HgL^– /lg ₁ = 16.58/ and lg ₁ = 17.7 are formed.     

The stability constants of TAR and PAR complexes

A discussion is given of the problem of ascribing dissociation constants in the hypothetical situation in which the protons of the hydroxy groups of TAR and PAR dissociate in the reverse of the normal order, and it is suggested that the o-hydroxy group should be regarded as intrinsically as acidic as the p-hydroxy group, and that the change in pK due to the internal hydrogen 'bonding is probably less than one unit.     

Macromolecular metal complexes as catalysts with improved stability

Polymer-bound tertiary amine–copper complexes and polymer-bound phosphite–rhodium complexes were studied as catalysts for oxidative coupling of phenols and hydroformylation of alkenes, respectively. The activity and stability of these catalysts could be tuned or optimized by adapting the structure of the ligands and by changing the distance between adjacent ligands along the polymer chains. The latter effect has been described in terms of strain in the intermediate chain segments in the copper complexes or enhancement of the effective local ligand concentration around the rhodium complexes. So-called immobilized homogeneous catalysts were obtained by end-grafting of both types of macromolecular catalysts on to inert and insoluble silica particles. These immobilized polymeric catalysts could easily be separated and recovered. Under proper conditions a grafted polymerbound imidazole–copper complex and a new type of polymer-bound triphenyl–phosphite–rhodium complex showed excellent stability in continuous processes.     

The metal complexes of some azo and azomethine dyestuffs : Determination of stability constants,and preparation of solid complexes

The stability constants of the complexes of 4-(2-pyridylazo)-resorcinol (I) with copper(II), cobalt-(II), zinc(Il), lead(ll), and uranium(VI) were determined by potentiometric titration in aqueous media, and were shown to have very high values, the stability constant of the copper(ll) complex approaching that of the copper(ll)-EDTA complex. The nickel(II) complex was shown to behave anomalously. The stability constants were also determined by this method in 1:1 dioxan/water, and the values obtained compared with those for the complexes of salicylidene-2-aminopyridine (II), 2-(o-hydroxy-phenyl-imino-methyl)-pyridine(III), and benzeneazoresorcino (IV). It is shown that chelation by (1) is terdentate, involving the pyridine nitrogen, the o-hydroxyl group and the azo nitrogen farthest from the heterocycle.The solid copper(II) complexes of these four ligands were prepared; in the solid complexes the azo nitrogen nearest the heterocycle plays a greater part than in the complexes in solution.     

The complexes of aluminium,gallium, and indium with calmagite: Evaluation of stepwise stability constants

Summary Calmagite [1-(1-hydroxy-4-methyl-2-phenyl azo)-2-naphthol sulphonic acid], dissociates in two steps. It forms violet complexes with Al³⁺, Ga³⁺ and In³⁺. The stepwise proton-ligand stability constants of calmagite and stepwise metal-ligand stability constants of these complexes were evaluated by potentiometric titration technique ofBjerrum andIrving andRossotti. The order of the stabilities of complexes is In³⁺ > Ga³⁺ > > Al³⁺.

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Zusammenfassung Camalgit [1-(1-Hydroxy-4-methyl-2-phenylazo)-2-naphtholsulfonsäure] dissoziiert in zwei Stufen und bildet violette Komplexe mit Al(III), Ga(III) und In(III). Die Konstanten der Dissoziationsstufen der freien Säure und die der Metallkomplexe wurden potentiometrisch nachBjerrum bzw.Irving undRossotti ermittelt. Die Stabilität der Komplexe nimmt in der Reihe In(III) > Ga(III) > Al(III) ab.

     

Determination of stability constants of metal(II)-methylcysteine and metal(II)-nitrilotriacetate-methylcysteine complexes with using a paper electrophoretic method

A method involving the use of paper ionophoresis is described for the study of the equilibria in mixed ligand complex systems in solution. Present method is based on the movement of a spot of metal ion under the electric field with the complexants added in the background electrolyte at pH 8.5. The concentration of primary ligand nitrilotriacetate (NTA) was kept constant while that of the secondary ligand methylcysteine was varied. The plot of log [methylcysteine] versus mobility were used to obtain information on the formation of mixed complexes and to calculate its stability constants. The binary equilibria metal(II)-methylcysteine and metal(II)-NTA have also been studied, since this is a prerequisite for the investigation of mixed complexes. The stability constants of the complexes Pb(II)-NTA-methylcysteine and UO₂ (II)-NTA-methylcysteine were found to be 3.03 ± 0.05 and 3.42 ± 0.09 (log K values) at ionic strength 0.01 M and a temperature of 35°C. Original Russian Text ? B.B. Tewari, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 151–155.