Kinetic study of the hydroxide ion attack on and DNA interaction with high spin iron(II) Schiff base amino acid chelates baering ONO donors

Kinetic study of some novel high spin Fe(II) complexes of Schiff base ligands derived from 5-bromsalicyaldehyde and amino acids with the OH^? ion and DNA has been carried out. Based on the kinetic data, the rate law and a plausible mechanism were proposed. Kinetic data of the base catalyzed hydrolysis imply pseudo first-order double stage process due to the presence of mer- and fac-isomers. The observed rate constants k _obs were correlated with the effect of a substituent R in the structure of ligands. The rate constants and activation parameters are in good agreement with stability constants of the studied complexes. Reactivity of the complexes towards DNA correlated well with the reported binding constants.     

Kinetic investigation of aquation of some Fe(II) Schiff base amino acid complexes

Kinetics of aquation of some Fe(II) Schiff base amino acid complexes was followed spectrophotometrically. The Schiff base ligands were derived from salicylaldehyde and isoleucine, leucine, serine, methionine, tryptophan, or histidine. The reaction was studied in aqueous media, aqua–propanol mixtures, and in the presence of different concentrations of KBr. Moreover, the activation parameters were calculated and discussed for structures and other physical properties observed. The reaction was acid catalyzed and the general rate equation was suggested as follows: rate = k_obs [complex], where k_obs = k₂ [H⁺]. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 372–379, 2010     

Kinetics and mechanism of the reaction of novel low spin Fe(II)-azo amino acid complexes with hydrogen peroxide in aqueous solutions and in aqua-methanol binary mixtures

Kinetics of Fe(II)-azo complexes derived from amino acids (DL-phenylalanine, DL-tryptophane, histidine and alanine) and p-nitroso aromatic substituted amines (N,N-dimethylamino-4-nitrosoaniline and N,N-dimethylamino-4-nitrosoaniline) with hydrogen peroxide in the aqueous solutions and under pseudo-first order conditions have been studied. The reaction exhibits two-stage kinetics. The reaction mechanism was proposed and discussed in terms of complex structure, pH and nature of the medium. The activation parameters and pK _a values were evaluated and correlated with the structural effects of the complexes.     

Kinetic studies on the formation of ternary complexes in the reaction of diaquonitrilotriacetatonickelate(II) with amino acids in aqueous solution

Summary Kinetics of formation of ternary complexes in the reaction of Ni(NTA)(H₂O) ₂ ^– with several amino acids, LH^± (glycine, -alanine, -alanine, L-valine and L-phenylalanine) have been studied by a pH indicator method using stopped-flow spectrophotometry. The results conform to 1/k_obs = 1/k + [H⁺]/ kKT_L where K is the equilibrium constant for formation of Ni(NTA)(–L)(H₂O)^2–, and k is the specific rate constant for the subsequent rate-determining ring-closure step leading to Ni(NTA)(=L)^2–. For the different amino acids studied, the k values decrease in the sequence: glycine > -alanine > L-phenylalanine > L-valine > -alanine. These k values areca. 1000 times lower than the values for complexation of Ni(NTA)(H₂O) ₂ ^– with NH₃ and imidazole and the spread in k values is much less than the pK_a values of the amino acids. The relative rates are enthalpy controlled and the S values are highly negative in conformity with ring closure as the rate determining step.     

Enthalpy and entropy changes associated with mixed ligand chelates of Cu(II) and Ni(II) with 4-methoxy picolinic acid N-oxide and some amino acids in aqueous medium

The stability constants of mixed complexes of Cu(II) and Ni(II) with 4-methoxy picolinic acid N-oxide, and glycine, α-alanine, proline and hydroxy-proline have been determined at various temperatures by the potentiometric method in 0·1 M ionic strength. The formation constants of the mixed complexes have been evaluated and are in good agreement with statistically expected values. The enthalpy and entropy values have been calculated from 1∶1∶1 stability constants temperature coefficient data. From the enthalpy values of the mixed complexes it may be concluded that the bond strengths are not equal to the average of the bond strengths inMA ₂ andMB ₂ type parent complexes. The entropy values have been found to be favourable for ternary complex formation.     

Kinetic exchange studies of metal ion substitution in EDTA chelates Fe(III)- UO2 EDTA exchange

A kinetic study of the exchange reaction between UO₂EDTA complex and Fe(III), at a constant ionic strength of 0.1, over the concentration range of 5×10^–3–1×10^–2 M of each reactant and pH 4.5–5.5 has been carried out radiometrically. The rate of the exchange process can be expressed by the equation: R=k₁[UO₂EDTA][Fe]+k₂[EDTA][H⁺]^–1. The activation parameters calculated were H^*=25.95 kJ mol^–1 and S^*=0.67 kJ mol^–1 K^–1.     

Kinetic and spectroscopic studies of an intermediate in the reaction of the diimine complex trisferrozineiron(II) with hydroxide ion in water and in aqueous methanol

Summary Kinetic and spectroscopic evidence is presented to support the postulate of a ligand-substituted intermediate in the reaction of the trisferrozineiron(II) anion with hydroxide ion in water and in aqueous methanol.     

Nickel(II) chelates of Schiff bases derived from isatin and chromone with amino acids and substituted hydrazines

Summary Nickel(II) complexes of the Schiff base derivatives of isatin with glycine, -alanine, anthranilic acid, S-methyl hydrazine carbodithioate, the ammonium salt of hydrazine carbodithioate, thiosemicarbazide, and benzoyl hydrazine, and nickel(II) complexes of 6-formyl-7-hydroxy-5-methoxy-2-methyl chromonelideneS-methyl hydrazine carbodithioate and benzoyl hydrazone, were prepared and characterized by elemental analysis, i.r., u.v.-vis spectra and magnetic measurements. All the complexes are octahedral.     

Ligand exchange and spin state equilibria of Fe(II)(N4Py) and related complexes in aqueous media

We report the characterization and solution chemistry of a series of Fe(II) complexes based on the pentadentate ligands N4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), MeN4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethanamine), and the tetradentate ligand Bn-N3Py (N-benzyl-1,1-di(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) ligands, i.e., [Fe(N4Py)(CH(3)CN)](ClO(4))(2) (1), [Fe(MeN4Py)(CH(3)CN)](ClO(4))(2) (2), and [Fe(Bn-N3Py)(CH(3)CN)(2)](ClO(4))(2) (3), respectively. Complexes 2 and 3 are characterized by X-ray crystallography, which indicates that they are low-spin Fe(II) complexes in the solid state. The solution properties of 1-3 are investigated using (1)H NMR, UV/vis absorption, and resonance Raman spectroscopies, cyclic voltammetry, and ESI-MS. These data confirm that in acetonitrile the complexes retain their solid-state structure, but in water immediate ligand exchange of the CH(3)CN ligand(s) for hydroxide or aqua ligands occurs with full dissociation of the polypyridyl ligand at low (<3) and high (>9) pH. pH jumping experiments confirm that over at least several minutes the ligand dissociation observed is fully reversible for complexes 1 and 2. In the pH range between 5 and 8, complexes 1 and 2 show an equilibrium between two different species. Furthermore, the aquated complexes show a spin equilibrium between low- and high-spin states with the equilibrium favoring the high-spin state for 1 but favoring the low-spin state for 2. Complex 3 forms only one species over the pH range 4-8, outside of which ligand dissociation occurs. The speciation analysis and the observation of an equilibrium between spin states in aqueous solution is proposed to be the origin of the effectiveness of complex 1 in cleaving DNA in water with (3)O(2) as terminal oxidant.     

Hydrophobic interaction effects on the kinetics of ligand substitution in binary aqueous mixtures at pentacyano(piperidine)ferrate(II) ion

The kinetics of piperidine replacement by pyridine at the pentacyano(piperidine)-ferrate(II) complex ion was studied under pseudo-first order conditions in binary aqueous mixtures of methanol, t-butanol, p-dioxane, and glycerol, from a mole fraction of co-solvent from 0 to about 0.15. The observed variations can be explained considering the degree of hydrophobic interaction between released ligand and water molecules which changes according to the structure-forming or struucture-breaking effect of added co-solvent on water.     

Hydrophilicity and acid hydrolysis of water-soluble antibacterial iron(II) Schiff base complexes in binary aqueous solvents

Kinetics of acid hydrolysis of seven antibacterial iron(II) Schiff base complexes has been studied. The Schiff base ligands were derived from sodium 2-hydroxybenzaldehyde-5-sulfonate and a series of amino acids. The hydrolysis rate is studied by spectrophotometric method and compared with complex hydrophilicity. Addition of the organic co-solvent, dimethylsulfoxide or n-propanol, significantly accelerates the hydrolysis.     

Kinetic studies on the bromate ion oxidation of 12-tungstocobaltate(II) in aqueous acid

The oxidation of Co^IIW by bromine(V) is a complex process involving an induction period. The reaction was found to be first-order in both [Co^IIW] and [Br^v], and exhibits a complex dependence on [H⁺]. These observations were successfully explained by considering HBrO₂, one of the intermediates formed in the direct but slow reaction between Co^IIW and bromine(V), as the reacting species. The first-order limiting dependence in [H⁺] was due to the involvement of a protic equilibrium of HBrO₂. The induction period appears due to the scavenging effect of Br^– inadvertently present in the medium. It appears to be the first report where HBrO₂ was found to be the reacting intermediate in the oxidation of metal ions and complexes by BrO^– ₃.     

Kinetics of photopolymerization of acrylamide initiated by copper (II)–bis(amino acid) chelates in aqueous solution. II

The kinetics of photopolymerization reactions of acrylamide initiated by copper (II)–bis(amino acid) chelates with amino acids glutamic acid, serine, or valine were studied at 30°C. The extent of monomer conversion increases with increased initiator concentration and falls off after reaching a maximum. Analysis of the results shows that for lower concentrations of the initiator, the rate of monomer disappearance is proportional to light absorption fraction f[monomer] and the square root of the intensity. At higher concentrations of the initiator, the rate of monomer disappearance is proportional to F_ε/[initiator]^1/2; the monomer exponent is 1.5 and the intensity exponent 0.5. Mutual termination of the radicals is proposed at lower concentrations of the initiator; at higher concentrations of the initiator termination of the initiator radical by the copper (II) complex along with mutual termination occurs. The initiator radical species is identified from flash photolysis studies of these complexes as the Cu(I)-coordinated radical. The effect of pH on the monomer conversion is explained. The data indicate a free-radical mechanism of polymerization and a reaction scheme is proposed for the polymerization reactions.     

Kinetic studies on the formation of ternary complexes in the reaction of diaquo-nitrilotriacetato-nickelate(II) and diaquo-anthranilato-N,N′-diacetato-nickelate(II) with amino acids in aqueous solution

Summary Kinetics of formation of ternary complexes from diaquo-nitrilotriacetatonickelate(II), [Ni(nta)(H₂O)₂]^–, and diaquoanthranilato-N, N-diacetatonickelate(II), [Ni(ada)-(H₂O₂] and amino acids have been studied by a pH indicator method using stopped-flow spectrophotontetry. The results conform to 1/k_obs=1/k+[H⁺]/kK·T_L, where K is the equilibrium constant for the formation of [Ni(A)(-L)(H₂O)]^2–(A=nta^3– or ada^3–) and k is the specific rate constant for the subsequent rate-determining ring closure leading to [Ni(A) (=L)]^2–. For the different amino acids, the k values decrease in the sequence: glycine>-alanine>L-phenylalanine>L-Valine>L-methionine>-alanine>sarcosine>N,N-dimethylglycine, and areca. 1000 times smaller than the k values for complexation of [Ni)(nta)(H₂O)₂]^– with monodentate ligands, such as NH₃ and imidazole. The spread of k values is much less than the pK_a values of the amino acids, and can be accounted for on the basis of the proposed mechanism. The relative rates are enthalpy controlled and high negative S values are commensurate with ring closure as the rate-determining step.     

Electron spin relaxation time of Ni(II) ion in hexapyrazole zinc(II) dinitrate at 300 K

Understanding the electron spin relaxation properties of paramagnetic species is a fundamental requirement to use them as a probe to measure distances between sites in biomolecules by electron paramagnetic resonance (EPR) spectroscopy. Even though Ni(II) ion is an essential trace element for many species, relaxation properties are not well understood. Herein, the polycrystalline sample of Ni(II) ion magnetically diluted in Zn(Pyrazole)₆(NO₃)₂ (Ni/ZPN) has been studied in detail by EPR spectroscopy to explore the electron spin relaxation time. Progressive continuous-wave (CW) EPR power saturation study on Ni/ZPN at 300 K yielded 907 mW as the P_1/2 value. The cavity constant (K_Q) has been calculated using tempol in PVA-BA glass matrix and the product of electron spin-lattice relaxation time (T₁) and spin–spin relaxation time (T₂) for Ni/ZPN at 300 K has been reported for the first time.     

Thermochemical study of the complex formation of copper(II) and nickel(II) iminodiacetates with amino acids in aqueous solutions

The formation of mixed-ligand complexes in the M(II)–Ida–L systems (M = Cu, Ni, L = His, Orn, Lys), where Ida is the iminodiacetic acid residue, was studied by pH-metry, calorimetry, and spectrophotometry. The thermodynamic parameters (logK, Δ_rG⁰, Δ_rH, Δ_rS) of formation of the complexes were determined at 298.15 K and the ionic strength I = 0.5 (KNO₃). The most probable mode of coordination of the chelating agent and the amino acid in the mixed-ligand complexes was elucidated.     

Kinetic investigation on the oxidation of nitrite by oxochromium(V) ion in aqueous and micellar systems

The kinetics of oxidation of nitrite by [O = Cr^V (5‐chlorosalen)]⁺ complex has been studied spectrophotometrically at [Cr^V] = 0.5 × 10^?3 M, [NO₂^?] = 0.01–0.1 M, [H⁺] = 0.0001–0.05 M, I = 0.15 M, and T = 25°C in the presence of cationic surfactant, cetyl pyridium chloride (CPC), and anionic surfactant, sodium dodecyl sulfate (SDS),in aqueous acidic medium. The oxygen atom transfer reaction from O = Cr^V to nitrite ion is influenced by the ionic nature of the micelle. The redox reaction is accelerated in presence of CPC and slowed down by 40 times in presence of SDS. The mechanism of the reaction involves an inner‐sphere process involving the formation of an intermediate followed by oxo transfer process. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 79–86 2004     

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