The Binding Affinity of Fe(III) to Aspartic Acid and Glutamic Acid Monohydroxamates

The solution spectra of Fe(III) complexes with aspartic acid (ASX) and glutamic acid (GLX) monohydroxamates were analyzed in the UV-Vis region for different complex species using STAR-94 programs in the pH range ¨ 1.0-4.0, at ionic strength (I) of 0.15 M NaCl and T = 25°C. Several monomeric complex species were obtained including some mixed hydroxo species. The reaction kinetics of the Fe(III)-(ASX or GLX) systems were carried out at I = 0.15 M NaCl and T = 25°C in the time range of the stopped-flow method. The pseudofirst-order rate constants were pH as well as T _L (analytic concentration of ASX or GLX) dependent, i.e. k _obs,i = A_i + B _i T_L (at a given pH _i ) where A_i and B_i are pH-dependent parameters.     

Iron(III) dihydrogenphosphate(I)

The structure of rhombohedral (R) iron(III) tris­[di­hydrogen­phosphate(I)] or iron(III) hypophosphite, Fe(H₂PO₂)₃, has been determined by single‐crystal X‐ray diffraction. The structure consists of [001] chains of Fe³⁺ cations in octa­hedral sites with symmetry bridged by bidentate hypophosphite anions.     

Chromium(III) Hydroxide Solubility in The Aqueous Na+-OH?-H2PO?4-HPO2?4-PO3?4-H2O System: A Thermodynamic Model

Chromium(III)-phosphate reactions are expected to be important in managing high-level radioactive wastes stored in tanks at many DOE sites. Extensive studies on the solubility of amorphous Cr(III) solids in a wide range of pH (2.8–14) and phosphate concentrations (10^–4 to 1.0 m) at room temperature (22±2)°C were carried out to obtain reliable thermodynamic data for important Cr(III)-phosphate reactions. A combination of techniques (XRD, XANES, EXAFS, Raman spectroscopy, total chemical composition, and thermodynamic analyses of solubility data) was used to characterize solid and aqueous species. Contrary to the data recently reported in the literature,⁽¹⁾ only a limited number of aqueous species [Cr(OH)₃H₂PO^–₄, Cr(OH)₃(H₂PO₄)^2–₂), and Cr(OH)₃HPO^2–₄] with up to about four orders of magnitude lower values for the formation constants of these species are required to explain Cr(III)-phosphate reactions in a wide range of pH and phosphate concentrations. The log K^o values of reactions involving these species [Cr(OH)₃(aq)+H₂PO^–₄⇌Cr(OH)₃H₂PO^–₄; Cr(OH)₃(aq)+2H₂PO^–₄⇌Cr(OH)₃(H₂PO₄)^2–₂; Cr(OH)₃(aq)+HPO^2–₄⇌Cr(OH)₃HPO^2–₄] were found to be 2.78±0.3, 3.48±0.3, and 1.97±0.3, respectively.     

Solution Properties of Azidokojatoiron(III) Complexes

The formation of iron(III) complexes with chelating azidokojate anions L⁻ was investigated in aqueous solutions as a function of the pH and the c(Fe³⁺):c(HL) molar ratio. Based on the stability constants, the distribution among the above complexes, [Fe(H₂O)₆]³⁺, and [Fe(H₂O)₅(OH)]²⁺ were calculated in solutions of various compositions. The complexes are redox stable in aqueous solutions both in the dark and in visible laboratory light. Properties of the investigated azidokojic acid and its iron(III) complexes are compared with those required for therapeutic applications as alternative iron chelators.     

Activity of metal chromate and phosphate supported on ion‐exchange resins toward hydrogen peroxide decomposition

The mixed resins, Dowex MR‐3 and MR‐12, in the H⁺/Cl⁻ form, and the cation resin, Dowex‐50W, in the H⁺ form, were used as a support for some metal chromate and phosphate salts. Similarly, anionic resin, Amberlite IRA‐400, in the Cl⁻ form, was used as a support for some metal chromate salts. The activity of these metal salt‐supported on four different resins toward hydrogen peroxide decomposition was investigated. The decomposition of H₂O₂, with these catalysts, was found to follow first‐order kinetics with respect to [H₂O₂]. Factors that affected the rate of reaction, such as mesh size of the support, amount of supported salt, and the electrostatic interactions, were investigated. With Ag(I)‐chromate supported on mixed resin MR‐3 in the Ag⁺/NO₃⁻ form, the rate of reaction was greater than that with the mixed resin MR‐12 in the same form. Moreover, the rate with Ag(I) chromate supported on the anion resin IRA‐400 in the R‐NO₃⁻ form was greater than mixed resins. Also, the rate with Fe(III) chromate supported on Amberlite IRA‐400 in the R‐CrO₄²⁻ form was greater than other counter‐anionic forms as well as Dowex‐50W resin in the metal ion form. However, Fe(III)‐chromate supported on cation resin R‐Fe³⁺ showed greater activity than other cationic forms. On the other hand, the rate with MR‐3 resin in the Na⁺/PO₄³⁻ form was greater than that in the presence of supported Fe(III) phosphate. However, the rate of reaction increased when Fe(III) was replaced by Ba(II). Iron(III) phosphate supported on Dowex‐50W resin in the Na⁺ form showed greater activity compared to MR‐3 resin in the Na⁺/PO₄³⁻ form. In the case of Fe(III) phosphate supported on mixed resin MR‐12, the rate was much greater than that with unsupported resin. However, when Ba(II) phosphate was incorporated instead of Fe(III) phosphate, the rate of reaction increased considerably. The activity of Fe(III) chromate is greater than that of Fe(III) phosphate supported on the same cation resin. Activation parameters were evaluated and a probable reaction mechanism was proposed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 667–675, 2000     

Study of equilibria and kinetics of the acid catalysed interaction of iron(III) with salicylaldehyde ando-hydroxyacetophenone

The equilibria and kinetics of the reaction of Fe^III with salicylaldehyde ando-hydroxyacetophenone, leading to 1∶1 chelate formation, have been studied at different temperatures (25–35°C) and ionic strength, I = 1.0 mol dm⁻³ (NaClO₄+HClO₄). A dual path mechanism involving both Fe _aq ³⁺ and Fe(OH) _aq ²⁺ species and undissociated free ligand (LH) is consistent with the experimental observations where [H⁺]≫[Fe]_T≫[L]_T (where [Fe]_T and [L]_T stand for total concentrations of iron and ligand respectively). The results conform to k_obs/B = k₁[H⁺]+k₂K_h where B = [Fe]_T/(K_h+[H⁺])+1/Q; K_h = hydrolysis constant of Fe _aq ³⁺ ; k₁, k₂ are the forward second order rate constants of Fe _aq ³⁺ and Fe(OH) _aq ²⁺ , respectively, and Q is the equilibrium constant of the reaction, Fe³⁺+LH⇋FeL²⁺+H⁺. Thermodynamic parameters for each of the steps have been determined. Fe(OH) _aq ²⁺ appears to react in a dissociative fashion (Eigen-Tamm mechanism), whilst Fe _aq ³⁺ appears to react through the associative inter-change (I_a) mechanism. The equilibrium constants (Q) obtained spectrophotometrically are compared with those obtained from kinetic studies. TMC 2638     

Complexation of magnesium and calcium ions with heparin

The acid-base properties of unfractionated heparin (H₄L) and the complexation of biometal ions (Mg²⁺ and Ca²⁺) with heparin in aqueous solutions have been studied by pH titration, using mathematical modeling methods in data processing. The heparin concentration is taken to be equal to the concentration of heparin disaccharide units. The formation constants of the protonated heparin species H_iL (i = 1, 2) have been estimated. The most abundant Mg²⁺-heparin and Ca²⁺-heparin complex species have been identified, and their formation constants have been estimated.     

Magnetite solubility and phase stability in alkaline media at elevated temperatures

A platinum-lined flowing autocláve facility was used to investigate the solubility behavior of magnetite (Fe₃O₄) in alkaline sodium phosphate and ammonium hydroxide solutions between 21 and 288°C. Measured iron solubilities were interpreted via a Fe(II)/Fe(III) ion hydroxo-, phosphato-, and ammino-complexing model and thermodynamic functions for these equilibria were obtained from a least-squares analysis of the data. A total of 14 iron ion species were fitted. Complexing equilibria are reported for 8 new species: Fe(OH)(HPO₄)^–, Fe(OH)₂(HPO₄)^2–, Fe(OH)₃(HPO₄)^2–, Fe(OH)(NH₃)⁺, Fe(OH)₂(PO₄)^3–, Fe(OH)₄(HPO₄)^3–, Fe(OH)₂(H₂PO₄)^–, and Fe(OH)₃(H₂PO₄)^3–. At elevated temperatures, hydrolysis and phosphato complexing tended to stabilize Fe(III) relative to Fe(II), as evidenced by free energy changes fitted to the oxidation reactions.

Equilibrium and kinetic studies of the Fe(III) complex formation with glycinehydroxamic acid

Spectrophotometric methods were utilized for stability constant determinations of the Fe(III) interaction with glycinehydroxamic acid (GX) at I = 0.15 M NACl and T = 25°C. Program SQUAD II was used to assess the absorbance data in the wavelength range 300–520 nm. Four constants were determined for 1:1:1, 1:1:0, 2:1:1 or 3:1:3 and 2:1:0 complex species in the pH range 1.0–7.5. The kinetics of the interactions of Fe(III) with GX were also studied in the pH range 1.0–3.0 by the stopped flow method. The observed rate constant at a given pH was k_obs = _A + BT_GX. The parameters A and B are functions of pH in the range 1.7–3.0 and only A is a function of pH in the range 1.0–1.7. The mechanism of complex formation was discussed in the light of the experimental results and the equilibrium study. It has been concluded that FeOH²⁺ is the reactive species in the complex formation of FeGXH³⁺ species while Fe(OH)₂⁺ is the reactive species in the complex formation of FeGX²⁺ species.     

Kinetic Studies of the Fe(III)/DI-2-Pyridyl Ketone Benzoylhydrazone Complex Reduction By Sulfite

The reactions of HSO^? ₃ with Fe(III) in the presence of di-2-pyridyl ketone benzoylhydrazone (DPKBH) have been investigated at 4.2-7.2 pH. The decomposition reaction of Fe(III)/DPKBH has been studied as a function of total sulfite concentration using spectrophotometric techniques. The kinetics are controlled by the equilibrium [Fe^III(DPKBH)(H₂O)]²⁺ ? [Fe^III(DPKBH)(OH)]⁺+H⁺, for which the hydrolysis constant was potentiometrically determined as 4.3 x 10^-5M, at (25.0 ± 0.1)°C and 1.5 x 10^-3M ionic strength. Both of those species undergo sulfite substitution and the significantly more labile species is the aqua complex. The formation constants of [Fe^III(DPKBH)(SO₃)] are 1.2 x 10⁴ at pH 4.2 and 1.9 x 10²M^-1 at pH 6.2. The limiting rate constants, k, at high HSO^? ₃ concentrations are 3.5 x 10^-2s^-1 and 1.4 x 10^-2s^-1, respectively, at pH 4.2 and 6.2, I = 1.3 x 10^-2M. The results are discussed with reference to the available literature data.     

Kinetics and mechanism of the formation of (1,8)bis(2-hydroxybenzamido)3,6-diazaoctaneiron(III) and its reactions with thiocyanate, azide, acetate, sulfur(IV) and ascorbic acid in solution, and the synthesis and characterization of a novel oxo bridged diiron(III) complex. The role of phenol–amide–amine coordination

The interaction of (1,8)bis(2-hydroxybenzamido)3,6-diazaoctane (LH₂) with iron(III) in acidic medium resulted in the formation of a mononuclear complex, Fe(LH₃)⁴⁺ which further yielded, [Fe(LH₂)]³⁺, [Fe(LH)]²⁺, and [FeL]⁺ due to protolytic equilibria. The formation of [Fe(LH₃)]⁴⁺ was investigated under varying [H⁺]_T (0.01–0.10 mol dm⁻³) and [Fe³⁺]_T (1.00 × 10⁻³–1.70 × 10⁻², [L]_T = 1.0 × 10⁻⁴ mol dm⁻³) (I = 0.3 mol dm⁻³, 10% MeOH + H₂O, 25.0 °C). The reaction was reversible and displayed monophasic kinetics; the dominant path involved Fe(OH)(OH₂) ₅ ²⁺ and LH ₄ ²⁺ . The mechanism is essentially a dissociative interchange (I _d) and the dissociation of the aqua ligand from the encounter complex, [Fe(OH₂)₅OH²⁺, H₄L²⁺] is rate limiting. The ligand binds iron(III) in a bidentate ([Fe(H₃L)]⁴⁺), tetradentate ([Fe(H₂L)]³⁺), pentadentate ([Fe(HL)]²⁺) and hexadentate fashion ([FeL]⁺) under varying pH conditions. Iron(III) promoted deprotonation of the amide and phenol moieties and chelation driven deprotonation of the sec-NH ₂ ⁺ of the trien spacer unit are in tune with the above proposition. The mixed ligand complexes, [Fe^III(LH)(X)] (X = N ₃ ⁻ , NCS⁻, ACO⁻) are also reversibly formed in solution thus indicating that there is a replaceable aqua ligand in the complex conforming to its octahedral coordination, [Fe(LH)(OH₂)]²⁺, the bound ligand is protonated at the sec-NH site. Despite the multidentate nature of the ligand the Fe^III complexes are prone to reduction by sulfur(IV) and ascorbic acid. The redox reactions of different iron(III) species, Fe^III(LH_i) which involved ternary complex formation with the reductants have been investigated kinetically as a function of pH, [S^IV]_T and [ascorbic acid]_T. The substantial pK perturbation of the bound ascorbate in [Fe(LH)(HAsc/Asc)]^+/0 (ΔpK _{{[Fe(LH)(HAsc)] − HAsc − }} > 6) is considered to be compelling evidence for chelation of HAsc⁻/Asc²⁻ leading to hepta coordination of iron(III) in the ascorbate complexes. A novel binuclear complex with composition, [Fe^III ₂C₂₀N₄H₃₅O₁₁ (NO₃)] has been synthesized and characterized by i.r., u.v.–vis, e.s.r., e.s.i.-Mass, ⁵⁷Fe Mossbauer spectroscopy and magnetic moment measurements. The complex was isolated as a mixture of two forms C ₁ and C ₂ with 75.3 and 24.7%, respectively as computed from Mossbauer data. The isomer shift (δ) (quadrupole splitting, ΔE _Q) are 0.32 mm s⁻¹ (0.75 mm s⁻¹) and 0.19 mm s⁻¹ (0.68 mm s⁻¹) for C ₁ and C ₂, respectively. The variable temperature magnetic moment measurements (10–300 K) of the sample showed that C ₁ is an oxo dimer exhibiting antiferromagnetic interaction between the iron(III) atoms (S ₁ = S ₂ = 5/2, J = − 120 cm⁻¹) while the dimer C ₂ is a high spin species (S ₁ = S ₂ = 5/2) and exhibits normal paramagnetism obeying the Curie law. The cyclic voltametry response of the sample (DMF, [TEAP] = 0.1 mol dm⁻³) displayed quasi-reversible responses at − 0.577 V and − 1.451 V (versus SCE). This is in tune with the fact that the C ₂ species reverts rapidly in solution to the relatively more stable oxo-bridged dimer (C ₁) which is reduced in two sequential steps: C₁ + e⁻ → [FeL]⁺ + Fe^II; [FeL]⁺ + e⁻ → Fe^IIL, the high labilility of the Fe^II complex is attributed to the irreversibility. The X-band e.s.r. spectrum of the polycrystalline sample at room temperature displayed a weak (unresolved) band at g = 4.2 and a strong band at g = 2.0 with hyperfine splitting due to the coordinated nitrogen (I = 1). At 77 K the band at g = 4.2 is intensified while that at g = 2 is broadened to the extent of near disappearance in agreement with the presence of the exchange coupled iron(III) centres. Electronic supplementary material Electronic supplementary material is available for this article at and accessible for authorised users. An erratum to this article is available at .     

Thermodynamics Analysis and Removal of P in a P-(M)-H2O System

In order to efficiently remove phosphorus, thermodynamic equilibrium diagrams of the P-H₂O system and P-M-H₂O system (M stands for Fe, Al, Ca, Mg) were analyzed by software from Visual MINTEQ to identify the existence of phosphorus ions and metal ions as pH ranged from 1 to 14. The results showed that the phosphorus ions existed in the form of H₃PO₄, H₂PO₄⁻, HPO₄²⁻, and PO₄³⁻. Among them, H₂PO₄⁻ and HPO₄²⁻ were the main species in the acidic medium (99% at pH = 5) and alkaline medium (97.9% at pH = 10). In the P-Fe-H₂O system ((P) = 0.01 mol/L, (Fe³⁺) = 0.01 mol/L), H₂PO₄⁻ was transformed to FeHPO₄⁺ at pH = 0–7 due to the existence of Fe³⁺ and then transformed to HPO₄²⁻ at pH > 6 as the Fe³⁺ was mostly precipitated. In the P-Ca-H₂O system ((P) = 0.01 mol/L, (Ca²⁺) = 0.015 mol/L), the main species in the acidic medium was CaH₂PO₄⁺ and HPO₄²⁻, and then transformed to CaPO₄⁻ at pH > 7. In the P-Mg-H₂O system ((P) = 0.01 mol/L, (Mg²⁺) = 0.015 mol/L), the main species in the acidic medium was H₂PO₄⁻ and then transformed to MgHPO₄ at pH = 5–10, and finally transformed to MgPO₄⁻ as pH increased. The verification experiments (precipitation experiments) with single metal ions confirmed that the theoretical analysis could be used to guide the actual experiments.     

Interaction Between the Low Molecular Mass Components of Blood Serum and the Vanadium(III)–2,2′-Bipyridine System

The complex species formed between vanadium(III)?C2,2??-bipyridine (Bipy) and the small blood serum bioligands lactic (HLac), oxalic (H₂Ox), citric (H₃Cit) and phosphoric (H₃PO₄) acids were studied in aqueous solution by means of electromotive forces measurements emf(H) at 25?°C and 3.0?mol?dm^?3 KCl as the ionic medium. The data were analyzed using the least-squares computational program LETAGROP, taking into account the hydrolytic products of vanadium(III) and the binary complexes formed. Formation of the complexes [V(Bipy)(Lac)]²⁺, [V(Bipy)(Lac)₂]⁺, [V(OH)₂(Bipy)(Lac)] and [V₂O(Bipy)₂(Lac)₂]^? were observed in the vanadium(III)?CBipy?CHLac system. Also, the species [V(Bipy)(HOx)]²⁺, [V(Bipy)(Ox)]⁺, [V(OH)(Bipy)(Ox)], [V(OH)₂(Bipy)(Ox)]^? and [V(OH)₃(Bipy)(Ox)]^2? were found in the vanadium(III)?CBipy?CH₂Ox system, the complexes [V(Bipy)(HCit)]⁺, [V(Bipy)(Cit)], [V(OH)(Bipy)(Cit)]^? and [V(OH)₂(Bipy)(Cit)]^2? were found in the vanadium(III)?CBipy?CH₃Cit system, and the species [V(Bipy)(H₂PO₄)]²⁺ and [V(Bipy)(HPO₄)]⁺ were detected in the vanadium(III)?CBipy?CH₃PO₄ system. The stability constants of these complexes were determined.     

Diagnostic cyclisation reactions which follow phosphate transfer to carboxylate anion centres for energised [M-H]- anions of pTyr-containing peptides

The low‐energy negative ion phosphoTyr to C‐terminal ‐CO₂PO₃H₂ rearrangement occurs for energised peptide [M–H]^– anions even when there are seven amino acid residues between the pTyr and C‐terminal amino acid residues. The rearranged C‐terminal ‐CO₂PO₂H(O^–) group effects characteristic S_Ni cyclisation/cleavage reactions. The most pronounced of these involves the electrophilic central backbone carbon of the penultimate amino acid residue. This reaction is aided by the intermediacy of an H‐bonded intermediate in which the nucleophilic and electrophilic reaction centres are held in proximity in order for the S_Ni cyclisation/cleavage to proceed. The ΔG_reaction is +184 kJ mol^?1 with the barrier to the S_Ni transition state being +240 kJ mol^?1 at the HF/6‐31 + G(d)//AM1 level of theory. A similar phosphate rearrangement from pTyr to side chain CO₂^– (of Asp or Glu) may also occur for energised peptide [M–H]^– anions. The reaction is favourable: ΔG_reaction is ?44 kJ mol^?1 with a maximum barrier of +21 kJ mol^?1 (to the initial transition state) when Asp and Tyr are adjacent. The rearranged species R¹‐Tyr‐NHCH(CH₂CO₂PO₃H^–)COR² (R¹ = CHO; R² = OCH₃) may undergo an S_Ni six‐centred cyclisation/cleavage reaction to form the product anion R¹‐Tyr(NH^–). This process has a high energy requirement [ΔG_reaction = +224 kJ mol^?1, with the barrier to the S_Ni transition state being +299 kJ mol^?1]. Copyright © 2011 John Wiley & Sons, Ltd.     

The reactivity of Ni(II) toward aspartic and glutamic monohydroxamates

The formation of complexes of Ni(II) with aspartic and glutamic acid hydroxamates was determined by potentiometric methods at I = 0.15 M NaCl and T = 25°C. The equilibrium study of Ni(II) with ASX or GLX revealed that the predominant species formed in solution were (M:L:H⁺): (1:1:0), (1:1:1), (2:1:0), and (2:1:1) in the whole pH range (～3–11). The formation of polymeric species was not observed. The octahedral structures were predicted in which the ligands act as tridentate ligands. The kinetics of complex formation between Ni(II) with ASX system as well as Ni(II) with GLX were also studied in a wide pH range. The observed rate constants for the Ni(II)‐hydroxamates were found to be dependent on the total concentration of hydroxamates at a given pH through the following relations: k_obs = Y₀ + Z(T_ASX) and k_obs = Y₀ + Z(T_GLX) + W(T_GLX)². The trans effect of the hydroxyl group present in the reacting species of Ni(OH)⁺ as well as a ring closure resulted from ligand chelation are introduced as explanations for the rate constants obtained for the reactions of Ni(II) with ASX or GLX. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 540–552, 2006     

Novel polydentate phosphonic acids: Protonation and stability constants of complexes with Fe(III) and Cu(II) in aqueous medium

The acido‐basic and the complexation properties of di‐, tri‐, and tetra‐phosphonic acids (H₆L1, H₈L2, and H₁₀L3) toward Fe(III) and Cu(II) were determined by potentiometric titration in aqueous media at 25.0 ± 0.1°C with constant ionic strength (0.1 M, NaClO₄). We have determined six, ten, and eight pK_a values for the di, tri, and tetra‐phosphonic acids, respectively. In acidic conditions, e.g., 0 ≤ pH ≤ 5; iron and copper presented a high affinity toward these ligands to give complex species. With the ligand H₁₀L3, [FeL3H₇], and [CuL3H₆]²⁻ were easily obtained at pH 1.8 and 2.7, respectively. We have determined ten stability constants for the H₁₀L3/Fe system and nine for the H₁₀L3/Cu one; six and four in the cases of H₈L2/Fe and H₈L2/Cu systems, respectively. Finally, five stability constants were calculated for the H₆L1/Fe system and four for the H₆L1/Cu one. We have not observed any insoluble species in these complexes in acidic medium as well as in alkaline solutions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:51–62, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20575     

COMPLEXES OF AMINOPHOSPHONATES PART 9.1 COPPER(II) COMPLEXES OF CIT RIC ACID DERIVATIVES

Abstract

Complex formation between copper(II) and 3-amino-3-phosphonoglutaric acid (Apga), an ambidentate aminophosphonate or citric acid derivative, was studied in aqueous solution by pH-potentiometry and EPR and electronic spectroscopy. Complexation with the parent molecules citric acid and tricarballylic acid was reinvestigated. The stoichiometries and stability constants of the complexes formed in these systems were determined at 25°C at an ionic strength of 0.20 mol dm^?3 (KCl). Stability constant data and spectroscopic results revealed that in the acidic pH range Apga behaves as a citric acid derivative, forming the phosphonate-bridged dimeric species Cu₂A₂H₂, while in the basic pH range, with decreasing proton competition at the amino binding site, it rearranges to yield mononuclear complexes involving aminophosphonate-like (NH₂, PO₃ ^2-, CO₂) coordination.     

Uptake of some lanthanides on γ-zirconium phosphate-phosphite and its 1,10-phenanthroline and 2,2-bipyridyl intercalated products

γ-Zirconium phosphate-phosphite, γ-Zr·PO₄·H₂PO₃·2H₂O, (γ-ZrPP), was prepared and characterized. Direct treatment of γ-zirconium phosphate-phosphite with an ethanol solution of 0.1M 1,10-phenanthrolin and 2,2'-bipyridyl gave the well defined composites, γ-Zr·PO₄·H₂PO₃(phen)_0.15·H₂O and γ-Zr·PO₄·H₂PO₃(bipy)_0.18·0.6H₂O respectively.K _d values of a mixture of lanthanide ions: La³⁺, Sm³⁺, Eu³⁺ and Yb³⁺ for the intercalated products and for γ-ZrPP in HNO₃ solution at room temperature and at pH 2 and 4 were determined by a radiotracer technique.¹⁴⁰La,^152mEu,¹⁵³Sm and¹⁷⁵Yb radioisotopes were used for the equilibration experiment using 500 μl (4.0·10⁻⁵ mmole) each of the solutions of the tracers as a mixture in 7.5 M HNO₃ solution at the desired pH with 0.1 g of γ-ZrPP and of the intercalated products. The selectivity order was found to be dependent on the nature of the ligand and on the pH. The 2,2'-bipyridyl product posseses, at pH 2 in general, a highK _d value, specially for Sm³⁺ (9815.9) compared to that of the 1,10-phenanthrolin product (3375.5) and to γ-ZrPP (419.8). This could be attributed to partial deintercalation of the 2,2'-bipyridyl at pH 2 and increasing of ionogenic groups.     

Complex Formation Equilibria of Unusual Seven-Coordinate Fe(EDTA) Complexes with DNA Constituents and Related Bio-relevant Ligands

Seven-coordinate Fe(EDTA)?CL complexes, where L represents a DNA constituent (uracil, uridine, thymine, thymidine and inosine), methylamine, ammonium chloride or imidazole, were investigated to resolve the solution chemistry of this system. The results show formation of 1:1 complexes with DNA constituents and the other ligands, supporting the hepta-coordination mode of Fe(III) ion. Stability constants of the complexes were measured by potentiometric titration at 25?°C and ionic strength 0.1 mol?L^?1 NaNO₃. The hydrolysis constant of [Fe(EDTA)(H₂O)]^? and the formation constants of the complexes formed in solution were calculated using the non-linear least-squares program MINIQUAD-75. The concentration distributions of the various complex species were evaluated as a function of?pH. The thermodynamic parameters ??H ⁰ and ??S ⁰, calculated from the temperature dependence of the equilibrium constants, were determined for the Fe(EDTA)?Curacil complex. The effect of dioxane as a solvent on the protonation constant of uracil, hydrolysis constants of [Fe(EDTA)(H₂O)]^?, and the formation constants of the Fe(EDTA)?Curacil complex are discussed.     

Complex Formation Equilibria of Unusual Seven Coordinate Fe(III) Complexes with DNA Constituents

Seven-coordinate Fe(III) complexes [Fe(dapsox)(H₂O)₂]⁺, where [dapsox = 2,6-diacetylpyridine-bis(semioxamazide)] is an equatorial pentadentate ligand with five donor atoms (2O and 3N), were studied with regard to their acid–base properties and complex formation equilibria. Stability constants of the complexes and the pK _a values of the ligands were measured by potentiometric titration. The interaction of [Fe(dapsox)(H₂O)₂]⁺ with the DNA constituents, imidazole and methylamine·HCl were investigated at 25 °C and ionic strength 0.1 mol·dm^?3 NaNO₃. The hydrolysis constants of the [Fe(dapsox)(H₂O)₂]⁺ cation (pK _a1 = 5.94 and pK _a2 = 9.04), the induced ionization of the amide bond and the formation constants of the complexes formed in solution were calculated using the nonlinear least-squares program MINIQUAD-75. The stoichiometry and stability constants for the complexes formed are reported. The results show the formation of 1:1 and 1:2 complexes with DNA constituents supporting the hepta-coordination mode of Fe(III). The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters ΔH° and ΔS° calculated from the temperature dependence of the equilibrium constants were investigated for interaction of [Fe(dapsox)(H₂O)₂] with uridine.