A bimetallic cyano-bridged complex based on nickel(II) and pentacyanidonitrosylferrate(II) precursors: characterization, crystal structure, and magnetic properties

A heterobimetallic cyano-bridged 1D coordination polymer of the composition [Ni(baepn)(μ-NC)Fe(CN)₃(NO)(μ-CN)]_n·3H₂O has been synthesized by the reaction of nickel(II) nitrate hexahydrate, baepn (baepn = N, N′-bis(2-aminoethyl)-1,3-propanediamine), and sodium nitroprusside dihydrate in a methanol–water mixture. The complex was characterized by physicochemical and spectroscopic methods. The crystal structure was established by single-crystal X-ray diffraction analysis. It reveals cyano-bridged heterometallic chains consisting of alternating arrays of Ni(II) and Fe(II) atoms, both being embedded in distorted octahedral environments. Low-temperature susceptibility measurements show the presence of weak antiferromagnetic exchange interactions between paramagnetic Ni(II) centers (J = −0.46 cm⁻¹) through long diamagnetic [Fe(CN)₅(NO)]²⁻ bridges. Spin state of the iron atom was established by ⁵⁷Fe M?ssbauer spectroscopy.     

Hemoglobin-stabilized tetranitrosyl binuclear iron complex with pyridine-2-yl in aqueous solutions

The tetranitrosyl iron complex with pyridine-2-yl [Fe₂(SC₅H₄N)₂(NO)₄] (1) has higher NO-donating activity in 3% aqueous solutions of DMSO (pH 7.0, 25 °C) than the organic NO donor, viz., adduct of NO with diethylenetriamine (NO-adduct). The NO concentration was determined by the spectrophotometric method based on the formation of an NO complex with hemoglobin (Hb). The apparent first-order rate constants of the studied reactions are (6.15±0.6)·10⁻¹ s⁻¹ and (0.8±0.08)·10⁻¹ s⁻¹ for complex 1 and the NO-adduct, respectively, at an Hb concentration of 2·10⁻¹ mol L⁻¹ and the ratio [NO donor]/[Hb] = 10. The effect of Hb and [NO donor]/[Hb] ratio on the rate of NO generation from a solution of complex 1 was studied. For a fourfold decrease in the concentration of complex 1 the reaction rate constant decreases to 0.5·10⁻⁴ s⁻¹, whereas the fourfold increase in the Hb concentration results in the stabilization of complex 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 732–736, April, 2007.     

Spin crossover in iron(II) complexes with tris(pyrazol-1-yl)methane

Mononuclear iron(II) coordination compounds with tris(pyrazol-1-yl)methane (HC(Pz)₃) described as [Fe{HC(Pz)₃}₂]A₂ × nH₂O, where A = Cl⁻, Br⁻, I⁻, 1/2 SO₄²⁻, n = 0–7, were synthesized. The compounds were studied by static magnetic susceptibility measurements, IR and UV/Vis spectroscopy, and powder X-ray diffraction. The crystal and molecular structures of all compounds were determined by single crystal X-ray diffraction.     

Structure and properties of μ<Subscript>2</Subscript>-<Emphasis Type="Italic">S</Emphasis>-[bis(benzenethiolato)tetranitrosyldiiron] in solution

Dinuclear iron tetranitrosyl complex with the composition [Fe₂(SPh)₂(NO)₄] (1) was synthesized and its single crystals and polycrystals were studied by X-ray diffraction, IR spectroscopy, and elemental analysis. The decomposition products of complex 1 were investigated by electrochemical method and mass spectrometry. The mass spectrum of a solution of complex 1 shows two groups of ions: the primary decomposition products of 1 in solution (the complex ions [Fe(SPh)(NO)₂(NO₂)]⁻, [Fe(SPh)₂(NO)]⁻, and [Fe(SPh)₂(NO)₂]⁻) and a series of the ions [FeO₂ + n(NO)]⁻ and [FeO₃ + n(NO)]⁻ (n = 0–4), which are formed in secondary reactions. The structures of the complexes, which were formed through the Fe-NO bond dissociation and the replacement of the NO ligand by aqua and oxygen ligands in complex 1, and the structure of the complex [FeO₃]⁻ were studied by quantum chemical modeling.     

Kinetic determination of silver at trace level based on its catalytic effect on a ligand substitution reaction

It is observed that Ag(I) catalyzes the rate of substitution of phenylhydrazine (PhNHNH₂) into hexacyanoferrate(II), producing a cherry red colored complex, [Fe(CN)₅PhNHNH₂]³⁻. The reaction was monitored at 488 nm leading to the formation of the complex under the conditions: [Fe(CN)₆]⁴⁻ (5.0 × 10⁻³ mol dm⁻³), PhNHNH₂ (2.0 × 10⁻³ mol dm⁻³), temperature (25 ± 0.1 °C), pH (2.8 ± 0.02), and ionic strength, I (0.02 mol dm⁻³), (KNO₃). Under optimum conditions, absorbance at fixed times (A _t ) is linearly related to Ag(I) in the concentration range 10.79–97.08 ng cm⁻³, in the presence of several diverse ions. The highest percentage error and relative standard deviations in the entire range of Ag(I) determination are found to be 2.5% and 0.16, with a detection limit of 8.75 ng cm⁻³ of silver(I). The experimental accuracies expressed in terms of percentage recoveries are in the range of 97.87–102.50. The method was successfully applied for the determination of Ag(I) in a few synthetic samples and found to be in good agreement with those obtained from atomic absorption spectrophotometry (AAS). The validity of the proposed method has also been tested for Ag(I) determination in spiked drinking water samples. The present catalytic kinetic method (CKM) is highly sensitive, selective, reproducible, and inexpensive. A review of recently published catalytic spectrophotometric methods for determination of Ag(I) has also been presented for comparison.     

Catecholase biomimetic catalytic activity of copper(II) complexes with 2-methyl-3-amino-(3H)-quinazolin-4-one

The oxidation of catechol by molecular oxygen in the presence of a catalytic amount of copper(II) complex with 2-methyl-3-amino-(3H)quinazoline-4-one (MAQ) and various anions (Cl⁻, Br⁻, ClO ₄ ⁻ , SCN⁻, NO ₃ ⁻ and SO ₄ ^– ) was studied. The catecholase biomimetic catalytic activity of the copper(II) complexes has been determined spectrophotometrically by monitoring the oxidative transformation of catechol to the corresponding light absorbing o-quinone (Q). The rate of the catalytic oxidation reaction was investigated and correlated with the catalyst structure, time, concentration of catalyst and substrate and finally solvent effects. Addition of pyridine or Et₃N showed a dramatic effect on the rate of oxidation reaction. Kinetic investigations demonstrate that the rate of oxidation reaction has a first order dependence with respect to the catalyst and catechol concentration and obeying Michaelis–Menten Kinetics. It was shown that the catalytic activity depends on the coordination environment of the catalyst created by the nature of counter anions bound to copper(II) ion in the complex molecule and follows the order: Cl⁻ > NO ₃ ⁻ > Br⁻ > SO ₄ ^– > SCN⁻ > ClO ₄ ⁻ . To further elucidate the catalytic activity of the complexes, their electrochemical properties were investigated and the catecholase mimetic activity has been correlated with the redox potential of the Cu²⁺/Cu⁺ couple in the complexes.     

Ferrocytochrome c and deoxyhemoglobin in the reaction with the iron cysteamine nitrosyl complex {Fe2[S(CH2)2NH3]2(NO)4}SO4·2.5H2O

By an example of the iron cysteamine nitrosyl complex {Fe₂[S(CH₂)₂NH₃]₂(NO)₄}SO₄··2.5H₂O (CAC), it was shown for the first time that the hydrolysis of this NO donor in the presence of ferrocytochrome c (cyt c ²⁺) affords the iron nitrosyl complex NO-cyt c ²⁺, which serves as the NO depot. The rate constant of NO release from CAC was determined from the kinetics of the formation of NO-cyt c ²⁺. At pH 3.0 the rate constant is (2.7±0.1)·10⁻³ s⁻¹. Ferrocytochrome c produces a less stabilizing effect on CAC than deoxyhemoglobin (Hb). Thus in the presence of cyt c ²⁺, the reaction is completed in 1 h, whereas NO is released from a solution of CAC (2·10⁻⁴ mol L⁻¹) in the presence of Hb during 40 h. The previously unknown stabilization of iron nitrosyl complexes by hemoglobin was found.     

Protonation of Chloro-, Bromo- and Iodo-pentacyanocobaltate(III) Complexes

The reactions between Fe(Phen)₃²⁺[phen = tris-(1,10) phenanthroline] and Co(CN)₅X³⁻ (X = Cl, Br or I) have been studied in aqueous acidic solutions at 25 °C and ionic strength in the range I = 0.001–0.02 mol dm⁻³ (NaCl/HCl). Plots of k₂ versus √I, applying Debye–Huckel Theory, gave the values −1.79 ± 0.18, −1.65 ± 0.18 and 1.81 ± 0.10 as the product of charges (Z_AZ_B) for the reactions of Fe(Phen)₃²⁺ with the chloro-, bromo- and iodo- complexes respectively. Z_AZ_B of ≈ −2 suggests that the charge on these Co^III complexes cannot be −3 but is −1. This suggests the possibility of protonation of these Co^III complexes. Protonation was investigated over the range [H⁺] = 0.0001 −0.06 mol dm⁻³ and the protonation constants K_a obtained are 1.22 × 10³, 7.31 × 10³ and 9.90 × 10² dm⁶ mol⁻³ for X = Cl, Br and I, respectively.     

Ion-pair formation in the outer-sphere electron transfer reactions between tris-(1, 10) phenanthroline iron(II) and the halopentacyanocobaltate(III) complexes in aqueous acidic solutions

The kinetics of the reactions between Fe(phen) ₃ ²⁺ [phen = tris–(1,10) phenanthroline] and Co(CN)₅X³⁻ (X = Cl, Br or I) have been investigated in aqueous acidic solutions at I = 0.1 mol dm⁻³ (NaCl/HCl). The reactions were carried out at a fixed acid concentration ([H⁺] = 0.01 mol dm⁻³) and the second-order rate constants for the reactions at 25 °C were within the range of (0.151–1.117) dm³ mol⁻¹ s⁻¹. Ion-pair constants K _ip for these reactions, taking into consideration the protonation of the cobalt complexes, were 5.19 × 10⁴, 3.00 × 10² and 4.02 × 10⁴ mol⁻¹ dm⁻³ for X = Cl, Br and I, respectively. Activation parameters measured for these systems were as follows: ΔH* (kJ K⁻¹ mol⁻¹) = 94.3 ± 0.6, 97.3 ± 1.0 and 109.1 ± 0.4; ΔS* (J K⁻¹) = 69.1 ± 1.9, 74.9 ± 3.2 and 112.3 ± 1.3; ΔG* (kJ) = 73.7 ± 0.6, 75.0 ± 1.0 and 75.7 ± 0.4; E _a (kJ) = 96.9 ± 0.3, 99.8 ± 0.4, and 122.9 ± 0.3; A (dm³ mol⁻¹ s⁻¹) = (7.079 ± 0.035) × 10¹⁶, (1.413 ± 0.011) × 10¹⁷, and (9.772 ± 0.027) × 10²⁰ for X = Cl, Br, and I respectively. An outer – sphere mechanism is proposed for all the reactions.     

Sorption behavior of Sn(II) onto Haro river sand from aqueous acidic solutions

The sorption behavior of Sn(II) onto Haro river sand has been examined with respect to nature of electrolyte, agitation time, dosage of sorbent and concentration of sorbate. Maximum sorption (95.5%) has been achieved from 0.034M hydrochloric acid solution after equilibrating sorbate (2·10⁻⁵M) and sorbent (50 mg) for 120 minutes at aV/W ratio of 90 cm³·g⁻¹. The kinetic data have been subjected to Morris-Weber and Lagergren equations. The kinetics of sorption proceeds a two stage process consisting of a relatively slow initial uptake followed by a much rapid increase in the sorption. The rate constant of intraparticle transport, K_d, comes out to be 8.75·10⁻⁸ mol·g⁻¹·min^−1/2 and the first order rate constant for sorption is 0.0416 min⁻¹. The sorption data of Sn(II) onto Haro river sand followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) type isotherms. The Langmuir constant,Q, related to sorption capacity and,b, related to sorption energy are computed to be 10.6±1.1 μmol·g⁻¹ and 1123±137 dm³·mol⁻¹, respectively. The D-R isotherm yields the values ofC _m=348±151 μmol·g⁻¹ and β=−0.01044±0.0008 mol²·kJ⁻² and ofE=6.9±0.3 kJ·mol⁻¹. In all three isotherms correlation factor (γ) is ≥0.99. The influence of common anions and cations on the sorption has been investigated. Zn(II), Mg(II), oxalate, Pb(II), Mn(II) and tartrate reduce the sorption significantly whereas Fe(II) causes substantial increase in the sorption. It is essential that all ions causing a decrease in the sorption of Sn(II) must be absent from the sorptive solution otherwise low sorption yields would result.     

Substoichiometric isotope dilution analysis of iron in biological materials by the 8-quinolinol-extraction

A highly precise and accurate method for the determination of minor amounts of iron by substoichiometric isotope dilution analysis is described. The constant amount of Fe(III) is substoichiometrically extracted with 2·10⁻⁴M oxine in chloroform from the aqueous phase of pH 9.2–10.0 containing 6·10⁻³M tartrate. The interfering ions such as Mn(II), Co(II), Ni(II), Cu(II), and Zn(II), can be removed by the preliminary extraction of Fe(III) from 7.5M hydrochloric acid solutions into isopropyl ether. The present method has been applied to the determination of iron in biological standard reference materials, i.e., the NBS Spinach (SRM-1570) and the NIES Pepperbush (SRM No. 1), and the results obtained are 548±9 ppm (NBS certified value: 550±20 ppm) and 193±4 ppm, respectively.     

Crystallochemical features of the anion varieties of aluminum and lithium binary hydroxide

Crystallochemical features of anion (Cl⁻, Br⁻, I⁻, NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ²⁻ ) varieties of the aluminum and lithium hydroxide were studied by using the aluminum and lithium binary hydroxide (LiOH·2Al(OH)₃·2H₂O) model in space group P6₃cm with the tetrahedral coordination of lithium. Atomic coordinates corresponding to the lowered lattice symmetry were refined. Institute of Solid State Chemistry and Processing of Mineral Raw Materials, Siberian Branch, Russian Academy of Sciences. Novosibirsk State Pedagogical University. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 5, pp. 158–170, September–October, 1994. Translated by T. Yudanova     

Kinetics of oxidation of N,N-bis(salicylaldehyde-1,2-diaminoethane) cobalt(II) complex by periodate. Evidence for the inhibiting effect of copper(II)

A kinetic study of the oxidation of [Co(H₂L)(H₂O)₂]²⁺ (H₂L = N,N-bis (salicylaldehyde-1,2-diaminoethane) Schiff base) by periodate in aqueous solution was performed over pH (2.3–3.4) range, (0.1–0.5) mol dm⁻³ ionic strength and temperatures 20–35 °C for a range of periodate and complex concentrations. The reaction rate showed a first-order dependence on both reactants and increased with pH over the range studied. The effects of Cu(II) and Fe(II) on the reaction rate were investigated over the (1.0–9.0) × 10⁻⁵ mol dm⁻³ range. The reaction was inhibited as the concentration of Cu(II) increased, and it was independent on Fe(II) concentrations over the ranges studied. An inner-sphere mechanism is proposed for the oxidation pathways of both the protonated and deprotonated Co^II complex species.     

Kinetic study of the promazine oxidation to promazine 5-oxide by trisoxalatocobaltate(III) in basic aqueous media

The kinetics of the oxidation of promazine by trisoxalatocobaltate(III) were studied in the presence of a large excess of the cobalt(III) in tris buffer solution using u.v.–vis spectroscopy ([Co^III] = (0.6 − 2) × 10⁻³ M, [ptz] = 6 × 10⁻⁵ M, pH = 6.6–7.8, I = 0.1 M (NaCl), T = 288−308 K, l = 1 cm). The reaction proceeds via two consecutive reversible steps. In the first step, the reaction leads to formation of cobalt(II) species and a stable cationic radical. In the second step, cobalt(III) is reduced to cobalt(II) ion and a promazine radical is oxidized to the promazine 5-oxide. Linear dependences of the pseudo-first-order rate constants (k ₁ and k ₂) on [Co^III] with a non-zero intercept were established for both redox processes. Rates of reactions decreased with increasing concentration of the H⁺ ion indicating that the promazine and its radical exist in equilibrium with their deprotonated forms, which are reactive reducing species. The activation parameters for reactions studied were as follows: ΔH^≠ = 44 ± 1 kJ mol⁻¹, ΔS^≠ = −100 ± 4 JK⁻¹ mol⁻¹ for the first step and ΔH^≠ = 25 ± 1 kJ mol⁻¹, ΔS^≠ = −169 ± 4 J K⁻¹ mol⁻¹ for the second step, respectively. Mechanistic consequences of all the results are discussed.     

Kinetic and mechanistic studies on the electron-transfer reactions between diaquabisethylenediaminecobalt(III) and ethylenediaminetetraacetatocobaltate(III) with promazine in acidic aqueous media

The kinetics of the electron-transfer reactions between promazine (ptz) and [Co(en)₂(H₂O)₂]³⁺ in CF₃SO₃H solution ([Co^III] = (2–6) × 10⁻³ m, [ptz] = 2.5 × 10⁻⁴ m, [H⁺] = 0.02 − 0.05 m, I = 0.1 m (H⁺, K⁺, CF₃SO ₃ ⁻ ), T = 288–308 K) and [Co(edta)]⁻ in aqueous HCl ([Co^III] = (1 − 4) × 10⁻³ m, [ptz] = 1 × 10⁻⁴ m, [H⁺] = 0.1 − 0.5 m, I = 1.0 m (H⁺, Na⁺, Cl⁻), T = 313 − 333 K) were studied under the condition of excess Co^III using u.v.–vis. spectroscopy. The reactions produce a Co^II species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k _obs) on [Co^III] with a non-zero intercept was established for both redox processes. The rate of reaction with the [Co(en)₂(H₂O)₂]³⁺ ion was found to be independent of [H⁺]. In the case of the [Co(edta)]⁻ ion, the k _obs dependence on [H⁺] was linear and the increasing [H⁺] accelerates the rate of the outer-sphere electron-transfer reaction. The activation parameters were calculated as follows: ΔH ^≠ = 105 ± 4 kJ mol⁻¹, ΔS ^≠ = 93 ± 11 J K⁻¹mol⁻¹ for [Co(en)₂(H₂O)₂]³⁺; ΔH ^≠ = 67 ± 9 kJ mol⁻¹, ΔS ^≠ = − 54 ± 28 J K⁻¹mol⁻¹ for [Co(edta)]⁻.     

Sensitive determination of nitric oxide in some rat tissues using polymer monolith microextraction coupled to high-performance liquid chromatography with fluorescence detection

A simple, sensitive, selective, and low-cost method is proposed for rapidly determining nitric oxide (NO) in some rat tissues. Polymer monolith microextraction (PMME) using a poly(methacrylic acid–ethylene glycol dimethacrylate) (MAA-EGDMA) monolithic column was combined with derivatization of NO using 1,3,5,7-tetramethyl-8-(3′,4′-diaminophenyl)-difluoroboradiaza-s-indacene (TMDABODIPY), and this was used to analyze the derivatives of NO by high-performance liquid chromatography (HPLC) with fluorescence detection at λ _ex/λ _em = 498/507 nm. The baseline separation of TMDABODIPY and its NO derivative is performed under simple conditions in which a C₁₈ column is used and eluted with 50 mmol L⁻¹ ethanolamine and methanol. The conditions for the extraction of NO derivatives were optimized. The limit of detection of NO was 2 × 10⁻¹² mol L⁻¹ (S/N = 3). The linearity range of the method was 9 × 10⁻¹¹−4.5 × 10⁻⁸ mol L⁻¹. The interday and intraday relative standard deviations were less than 5%. The proposed method was successfully applied to the determination of NO levels in some rat tissue samples including heart, kidney, and liver with recoveries varying from 87.1 to 95.2%.     

Potentiometric Determination of Menadione (Vitamin K3)

 The construction and electrochemical response characteristics of poly(vinyl) chloride matrix membrane sensors for menadione (vitamin K₃) are described. Membranes incorporating the ion association complexes of menadione anion with bathophenanthroline nickel(II) and iron(II) as electroactive materials show linear response for menadione over the range 10⁻¹–10⁻⁵ M with anionic slopes of 58.2–51.4 mV per concentration decade. Both sensors exhibit fast response time (20–30 s), low detection limit (2 × 10⁻⁵ M), good stability (4–6 weeks) and selectivity coefficient (10⁻¹–10⁻³). Direct potentiometric determination of menadione under static and hydrodynamic mode of operations shows average accuracies of 98.8 and 98.5% with relative standard deviations of 0.6% and 1.3%, respectively. Application of the method for the determination of menadione in human plasma gives favourable results compared with those obtained by the standard spectrophotometric method. Received February 26, 2001. Revision October 1, 2001.     

Adsorption of Cu(II), Cd(II), Pb(II), Cr(VI) by double hydroxides on the basis of Al oxide and Zr, Sn, and Ti oxides

It was studied the equilibrium adsorption and adsorption kinetics of Cu(II), Cd(II), Pb(II), and Cr(VI) by composite hydroxides formed by Me _x O _y · nH₂O and Me_0.4–0.7Al_0.6–0.3O _y · nH₂O, where Me = Zr, Sn and Ti. It was estimated the values of the diffusion coefficients of adsorbed ions Cu(II) and Cr(VI) from kinetic values. It was established that the estimated diffusion coefficients of adsorbed ions Cu(II) are in the range 0.4 × 10⁻¹²–2.5 × 10⁻¹² m²/s for individual hydroxides and 1.2 × 10⁻¹²–2.8 × 10⁻¹² m²/s for double hydroxides. The obtained values of diffusion coefficients Cr (VI) for double hydroxides are 0.1 × 10⁻¹⁰–0.4 × 10⁻¹⁰ m²/s.     

Competition Between O2 and H2O2 in the Oxidation of Fe(II) in Natural Waters

The oxidation rates of nanomolar levels of Fe(II) in seawater (salinity S = 36.2) by mixtures of O₂ and H₂O₂ has been measured as a function of pH (5.8–8.4) and temperature (3–35∘C). A competition exists for the oxidation of Fe(II) in the presence of both O₂ (μ mol⋅L⁻¹ levels) and H₂O₂ (nmol⋅L⁻¹ levels). A kinetic model has been applied to explain the experimental results that considers the interactions of Fe(II) with the major ions in seawater. In the presence of both oxidants, the hydrolyzed Fe(II) species dominate the Fe(II) oxidation process between pH 6 and 8.5. Over pH range 6.2–7.9, the FeOH⁺ species are the most active, whereas above pH 7.9, the Fe(OH)⁰₂ species are the most active at the levels of CO²⁻₃ concentration present in seawater. The predicted Fe(II) oxidation rate at [Fe(II)]₀ = 30nmol⋅L⁻¹ and pH = 8.17 in the oxygen-saturated seawater with [H₂O₂]₀ = 50nmol⋅L⁻¹ (log ₁₀ k = −2.24s⁻¹) is in excellent agreement with the experimental value of log ₁₀ k = −2.29s⁻¹ ([H₂O₂]₀ = 55nmol⋅L⁻¹, pH = 8).