Electrolytically generated sulfur dioxide anion radical S2O·−4, its absorption coefficient and some of its decay reactions

The electrochemical reduction of SO₂ in dimethylformamide at Pt electrodes finally leads to the red species S₃O^2?₆ via the blue complex S₂O^·?₄. The UV-VIS absorption coefficients are determined: ?(S₂O^·?₄) = (224 ± 25) × 10⁵ cm² mol^?1; ?(S₃O^2?₆) = (0.64 + 0.07) × 10⁵ cm² mol^?1. A calculation of the complexing constant of SO₂ with free SO^·?₂ radical based on potential shifts confirms this constant to be in the range of 200–700 1 mol^?1.Two potentiometric titration methods (viz: with allylbromide and tetraethylammoniumtribromide) for analysis of electrolytically generated S^III-oxo-anions in DMF are presented. Reactions of those anions with aromatic aldehydes and trials for trapping of possibly formed SO are described.     

An electsochemical study of copper(II) nitrate and perchlorate in n,n-dimethylformamide

Polarographic, cyclic voltammetric and controlled-potential coulometric studies of copper(II) nitrate and perchlorate in dimethylformamide are reported. Copper(II) in copper(II) perchlorate solutions is directly reduced in a 2e step to copper metal at platinum electrodes and to a copper amalgam at mercury electrodes. Copper(II) in the presence of nitrate forms a complex of composition Cu(N0₃)₂ in DMF; the dissociation constant, measured polarographically, is 9 × lO^-5. The copper(II) nitrate complex is electrochemically reduced in two steps consisting of a reversible dissociation of the complex followed by direct reduction of copper(II) ion to copper(0). The diffusion coefficients of copper(II) ion and the copper(II) nitrate complex are 4.91 × lO^-6 cm² s^-1 and 4.33 × 10^-6 cm² s^-1, respectively.     

The (CF3S)2N. radical : preparation,dimerization, ESR-studies

The Bis (trifluormethylmercapto) amino radical (CF₃S)₂N· has been prepared by oxidation of Bis (trifluormethylmercapto) amine, (CF₃S)₂NH with activated lead diooxide in CCl₃F solution at room temperature. The 10^?5 – 10^?6 molar solution of the radical shows in the ESR- spectrum a triplett of septetts with a isotropic nitrogen hyperfine splitting constant a(¹⁴N) = 13,2 G, a(¹⁹F) = 1.95 G, indicating that the radical is a planar sp² species where the unpaired electron is located predominantly in the nitrogen 2p orbital. It is suggested that in solution an thermal equilibrium exists between the (CF₃S)₂ N radical and its dimer Tetrakis (trifluormethylmercapto)-hydrazine:

Aspects of preparation as well as thermodynamic and kinetic details of the hydrazine (NN bond strength 7 kcal/mol^?1) and the equilibrium, which can be followed by ESR-spectroscopy will be given.     

Matrixreaktion von GeO mit F2. IR-spektroskopischer nachweis von molekularem OGeF2

GeO reacts with F₂ in an argon matrix after photolysis with a high-pressure mercury lamp to form OGeF₂. Isotopic splitting (¹⁶O/¹⁸O and ⁷⁰Ge/⁷²Ge/⁷⁴Ge) and force constant calculations show that the fundamentals observed can be assigned to a planar molecule OGeF₂. The value of the force constant of the GeO double bond, 7.43 × 10² N m^?1, is as expected (GeO₂ 7.32 × 10² N m^?1), but the GeF bond is unexpectedly weak (f_GeF = 5.01 × 10² N m^?1).     

Kinetics and mechanism of the oxidation of iron(II) ion by chlorine dioxide in aqueous solution

The mechanism by which an excess of iron(II) ion reacts with aqueous chlorine dioxide to produce iron(III) ion and chloride ion has been determined. The reaction proceeds via the formation of chlorite ion, which in turn reacts with additional iron(II) to produce the observed products. The first step of the process, the reduction of chlorine dioxide to chlorite ion, is fast compared to the subsequent reduction of chlorite by iron(II). The overall stoichiometry is The rate is independent of pH over the range from 3.5 to 7.5, but the reaction is assisted by the presence of acetate ion. Thus the rate law is given by At an ionic strength of 2.0 M and at 25°C, k_u = (3.9 ± 0.1) × 10³ L mol^?1 s^?1 and k_c = (6 ± 1) × 10⁴ L mol^?1 s^?1. The formation constant for the acetatoiron(II) complex, K_f, at an ionic strength of 2.0 M and 25°C was found to be (4.8 ± 0.8) × 10^?2 L mol^?1. The activation parameters for the reaction were determined and compared to those for iron(II) ion reacting directly with chlorite ion. At 0.1 M ionic strength, the activation parameters for the two reactions were found to be identical within experimental error. The values of ΔH? and ΔS? are 64 ± 3 kJ mol^?1 and + 40 ± 10 J K^?1 mol^?1 respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 554–565, 2004     

Synthesis, electrochemical, magnetic, catalytic and antimicrobial studies of N-functionalized cyclam based trinuclear copper(II) and nickel(II) complexes

Trinuclear copper(II) and nickel(II) complexes have been prepared by using Schiff base ligands derived from 1,8-[bis(3-formyl-2-hydroxy-5-methyl) benzyl]-4,11-dimethyl-l,4,8,11-tetraazacyclotetradecane, and 1,8-[bis(3-formyl-2-hydroxy-5-bromo)benzyl]-4,11-dimethyl-l,4,8,11-tetraazacyclotetradecane with aliphatic and aromatic diamines. All the complexes were characterized by elemental and spectroscopic analysis. Electrochemical studies of the copper(II) complexes in DMF solution show three irreversible one electron reduction process around E _pc  ¹ = ?0.59 to ?0.80 V, E _pc  ² = ?0.89 to ?1.14 V and E _pc  ³ = ?1.17 to ?1.29 V, and for nickel(II) complexes it is around E _pc  ¹ = ?0.63 to ?0.77 V, E _pc  ² = ?1.20 to ?1.35 V and E _pc  ³ = ?1.60 to ?1.74 V. ESR spectra and magnetic moments of the trinuclear Cu(II) complexes show the presence of antiferromagnetic coupling. Cryomagnetic investigation of the trinuclear copper(II) complexes show that the observed ?2J values are in the range of 116–178 cm^?1. The rate constants for hydrolysis of 4-nitrophenylphosphate by the complexes are in the range of 2.68 × 10^?2 to 9.81 × 10^?2 min^?1. The rate constants values for the catecholase activity of the copper(II) complexes fall in the range of 3.03 × 10^?2 to 9.32 × 10^?2 min^?1. All the complexes.     

The collisional quenching of O2*(1Δg) by NO and CO2

Rate coefficients for the collisional quenching of O₂^*(¹Δ_g) by NO and CO₂ at 2–8 torr and 300 K have been determined. k_NO = (2.48 ± 0.23) × 10^?17 cm³ molecule^?1 s^?1 and

= (2.56 ± 0.12) × 10^?18 cm³ molecule^?1 s^?1.     

Interaction of Polystyryl Radical with Tris Azido-Iron(III) Complex

The polymerization of styrene initiated by 2,2′-azobisisobutyro-nitrile (AIBN) had been studied in N, N-dimethylformamide (DMF) at 60°C in presence of tris azido-iron(III) complex. The complex was prepared in situ by mixing solid sodium azide with hexakis(N, N-dimethylformamide)iron(m) perchlorate, [Fe(DMF)₆] (ClO₄)₃, in the ratio 3:1. The nature of the complex formed was established by Job's method. The equilibrium constant for Fe³⁺ + 3N₃ ^? ? Fe(N₃)₃ determined by the limiting logarithmic method is 6.14 ± 10⁶ liter³/mole³. The velocity constant for the polystyryl radical towards the complex is 3.13 ± 10⁴ liter/mole-sec.     

MP2, DFT‐D,and PCM study of the HMB–TCNE complex: Thermodynamics,electric properties,and solvent effects

Geometry, thermodynamic, and electric properties of the π‐EDA complex between hexamethylbenzene (HMB) and tetracyanoethylene (TCNE) are investigated at the MP2/6‐31G* and, partly, DFT‐D/6‐31G* levels. Solvent effects on the properties are evaluated using the PCM model. Fully optimized HMB–TCNE geometry in gas phase is a stacking complex with an interplanar distance 2.87 × 10^?10 m and the corresponding BSSE corrected interaction energy is ?51.3 kJ mol^?1. As expected, the interplanar distance is much shorter in comparison with HF and DFT results. However the crystal structures of both (HMB)₂–TCNE and HMB–TCNE complexes have interplanar distances somewhat larger (3.18 and 3.28 × 10^?10 m, respectively) than our MP2 gas phase value. Our estimate of the distance in CCl₄ on the basis of PCM solvent effect study is also larger (3.06–3.16 × 10^?10 m). The calculated enthalpy, entropy, Gibbs energy, and equilibrium constant of HMB–TCNE complex formation in gas phase are: ΔH⁰ = ?61.59 kJ mol^?1, ΔS = ?143 J mol^?1 K^?1, ΔG⁰ = ?18.97 kJ mol^?1, and K = 2,100 dm³ mol^?1. Experimental data, however, measured in CCl₄ are significantly lower: ΔH⁰ = ?34 kJ mol^?1, ΔS = ?70.4 J mol^?1 K^?1, ΔG⁰ = ?13.01 kJ mol^?1, and K = 190 dm³ mol^?1. The differences are caused by solvation effects which stabilize more the isolated components than the complex. The total solvent destabilization of Gibbs energy of the complex relatively to that of components is equal to 5.9 kJ mol^?1 which is very close to our PCM value 6.5 kJ mol^?1. MP2/6‐31G* dipole moment and polarizabilities are in reasonable agreement with experiment (3.56 D versus 2.8 D for dipole moment). The difference here is due to solvent effect which enlarges interplanar distance and thus decreases dipole moment value. The MP2/6‐31G* study supplemented by DFT‐D parameterization for enthalpy calculation, and by the PCM approach to include solvent effect seems to be proper tools to elucidate the properties of π‐EDA complexes. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Extractive-spectrophotometric determination of traces of copper(II) with 4-(p-nitrophenylazo)-2-amino-3-pyridinol

A new extractive-spectrophotometric method for determination of copper(II) with 4-(p-nitrophenylazo)-2-amino-3-pyridinol is proposed. The established stoichiometry and extraction constant are 2:1 ligand:metal and ?1.55, respectively. The molar absorptivity of the complex is 5.19 × 10⁴ liters mol^?1 cm^?1 at 560 nm and Sandell's sensitivity is 1.2 ng cm^?2. The best conditions for determination and effect of other ions are studied. The method proposed is applied in the determination of copper in whisky, liver of fish, and seawater.     

Sensitive determination of the endocrine disruptor bisphenol A at ultrathin film based on nanostructured hybrid material SiO<Subscript>2</Subscript>/GO/AgNP

In this work, we described an electrochemical sensor using a nanocomposite based on graphene oxide (GO), silver nanoparticles (AgNP), and disordered mesoporous silica (SiO₂), which was used for the determination of bisphenol A in water samples. Initially, the hybrid material SiO₂/GO was synthesized via sol-gel process, subsequently decorated with AgNP with an approximate 20 nm particle size prepared directly on the surface of the SiO₂/GO using N, N-dimethylformamide (DMF) as an agent reducer. A glassy carbon electrode was modified with SiO₂/GO/AgNP and used in developing a sensitive electrochemical sensor for the determination of bisphenol A in phosphate buffer 0.1 mol L^?1 (pH 7.0). The detection limit was 45.2 nmol L^?1 with a linear response range between 1.0 × 10^?7 and 2.6 × 10^?6 mol L^?1 and a sensitivity of 1.27 × 10^?7 A mol^?1 L. Finally, the optimized electrochemical sensor was used for the quantitation of endocrine interfering in natural waters.     

4-氯-2-(1H-咪唑并[4,5-f][1,10]菲咯啉)苯酚铜(Ⅱ)配合物的晶体结构及其与DNA的相互作用

利用菲咯啉酮衍生物4-氯-2-(1H-咪唑并[4,5-f][1,10]菲咯啉)苯酚(HL)设计合成了一种新的单核铜配合物[Cu(L)(5-Cl-sal)(DMF)]ClO_4·DMF(5-Cl-Hsal=5-氯-水杨醛),用元素分析和X射线单晶衍射等手段对配合物进行了表征。该配合物晶体属三斜晶系,P1空间群。用紫外吸收光谱、荧光光谱和凝胶电泳等方法研究了配合物与DNA的相互作用。结果表明,配合物以插入方式与CT-DNA结合,结合常数为1.02×10~3 L·mol~(-1)。同时配合物也能较大程度淬灭EB-DNA复合物的荧光,表观键合常数为4.37×10~5L·mol_(-1),略小于经典键合常数107 L·mol~(-1)。淬灭机理为动态淬灭。凝胶电泳实验研究表明配合物在H_2O_2存在下可将pBR322质粒DNA切割为开环缺口型DNA和线型DNA,配合物浓度越大,切割效果越好。机理研究显示,配合物切割DNA的反应是由羟基自由基(·OH)和单线态氧(~1O_2)作为活性物种的氧化切割过程。     

Lifetimes of the vibronic Ã2A1 states of H2S+

Lifetimes have been measured for the Σ and Π vibronic òA₁ states of H₂S⁺ by studying the decay curves of the òA₁ (0, υ′₂, 0) → X? ²B₁ (0, υ″₂, 0) emission bands. The vibronic òA₁ states are produced via excitation of H₂S molecules by 150 eV electrons. The Σ sublevels 1 ? υ′₂ ? 7 and the Π sublevels 3 ? υ′₂ ? 6 have been considered. Predissociation occurs in the Σ sublevels for υ′₂ ? 7 and in the Π sublevels for υ′₂ ? 6. The obtained radiative lifetimes for the non-predissociated Σ and Π sublevels are around 4.2(±0.4) × 10^?6 s and 5.6(±0.5) × 10^?6 s respectively. For the predissociated Σ(0, 7, 0) and Π(0, 6, 0) levels the corresponding lifetimes are 2.3(±0.3) × 10^?6 s and 1.6(±0.3) × 10^?6 s respectively. The rate constant for collisional deactivation (quenching) of the vibronic òA₁ states by H₂S molecules was found to equal 2.3(±0.3) × 10^?9 cm³ mol^?1 s^?1.     

4-氯-2-(1H-咪唑并[4,5-f][1,10]菲咯啉)苯酚铜(Ⅱ)配合物的晶体结构及其与DNA的相互作用

利用菲咯啉酮衍生物4-氯-2-(1H-咪唑并[4,5-f][1,10]菲咯啉)苯酚(HL)设计合成了一种新的单核铜配合物[Cu (L)(5-Cl-sal)(DMF)]ClO₄·DMF (5-Cl-Hsal=5-氯-水杨醛),用元素分析和X射线单晶衍射等手段对配合物进行了表征。该配合物晶体属三斜晶系,P1空间群。用紫外吸收光谱、荧光光谱和凝胶电泳等方法研究了配合物与DNA的相互作用。结果表明,配合物以插入方式与CT-DNA结合,结合常数为1.02×10³ L·mol^-1。同时配合物也能较大程度淬灭EB-DNA复合物的荧光,表观键合常数为4.37×10⁵ L·mol^-1,略小于经典键合常数10⁷ L·mol^-1。淬灭机理为动态淬灭。凝胶电泳实验研究表明配合物在H₂O₂存在下可将pBR322质粒DNA切割为开环缺口型DNA和线型DNA,配合物浓度越大,切割效果越好。机理研究显示,配合物切割DNA的反应是由羟基自由基(·OH)和单线态氧(¹O₂)作为活性物种的氧化切割过程。     

Synthetic and kinetic studies on copper(II), nickel(II) and cobalt(III) complexes of 1,4,7,10,13-pentaazacyclohexadecane ([16]aneN5)

Summary The pentadentate macrocycle 1,4,7,10,13-penta-azacyclo-hexadecane [16]aneN₅=(3)=L} has been prepared and a variety of copper(II), nickel(II) and cobalt(III) complexes of the ligand characterised. The copper complex [CuL](ClO₄)₂, on the basis of its d-d spectrum, appears to be square pyramidal, while [NiL(H₂O)](ClO₄)₂ is octahedral. The copper(II) and nickel(II) complexes dissociate readily in acidic solution and these reactions have been studied kinetically. For the copper(II) complex, rate=k_H[complex][H⁺]² with k_H =4.8 dm⁶ mol^–2s^–1 at 25 °C and I=1.0 mol dm^–3 (NaClO₄) with H=43 kJ mol^–1 and S ₂₉₈ =–89 JK^–1 mol^–1. Dissociation rates of the copper(II) complexes increase with ring size in the order: [15]aneN₅ < [16]aneN₅ < [17]aneN₅. For the dissociation of the nickel(II) complex, rate=k_H[Complex][H⁺] with k_H=9.4×10^–3 dm³mol^–1 s^–1 at 25 °C and I =1.0 mol dm^–3 (NaClO₄) with H=71 kJ mol^–1 and S ₂₉₈ =–47 JK^–1mol^–1.The cobalt(III) complexes, [CoLCl](ClO₄)₂, [CoL(H₂O)]-(ClO₄)₃, [CoL(NO₂)](ClO₄)₂, [CoL(DMF)](ClO₄)₃ (DMF=dimethylformamide) and [CoL(O₂CH)](ClO₄)₂ have been characterised. The chloropentamine [CoCl([16]aneN₅)]²⁺ undergoes rapid base hydrolysis with k_OH=1.1× 10⁵dm³ mol^–1s^–1 at 25°C and I=0.1 mol dm^–3 (H=73 kJ mol^–1 and S ₂₉₈ =98 JK^–1 mol^–1). Rapid base hydrolysis of [CoL(NO₂)]²⁺ is also observed and the origins of these effects are considered in detail.     

Studies on the reaction N + N3 → N2(B 3Πg) + N2(X 1Σ+g)

Strongly enhanced N₂ first positive emission N₂(B ³Π_g → A ³Σ⁺_u) has been observed on addition of N atoms into a flowing mixture of Cl and HN₃. The dependence of the emission intensity on N atom concentration gave a rate constant for the reaction N + N₃ → N₂(B ³Π_g) + N₂(X ¹Σ⁺_g) of _i(1.6 ± 1.1) × 10^?11 cm³ molecule^?1 s^?1. That for the reaction Cl + HN₃ → HCl + N₃ is (8.9 ± 1.0) × 10^?13 cm³ molecule^?1 s^?1 from the decay of the emission. Comparison of the emission intensity in ClHN₃ with that in ClHN₃N gave the rate constant of the reaction N₃ + N₃ → N₂(B ³Π_g) + 2N₂(X ¹Σ⁺_g) as 1.4 × 10^?12 cm³ molecule^?1 s^?1 on the assumption that N + N₃ yields only N₂(B ³Π_g) + N₂(X ¹Σ⁺_g).     

Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media

Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML²⁺ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (k_obs) showing acid dependence; for the nickel(II) complex (k_obs)=k_O+k_H[H⁺], the k_o path is however absent with the copper(II) complex. At 60°C (I=0.1M) the k_H values areca 10^–4 M^–1 s^–1 for both complexes; k _H ^Cu /k _H ^Ni =ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol^–1; nickel(II) complex, 35.6±1.5 kJ mol^–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK^–1 mol^–1 and for nickel(II), –208.1 ±5.6 JK^–1 mol^–1] which are much higher than the entropy of solvation of Ni²⁺ (ca. –160 JK^–1 mol^–1) and Cu²⁺ (ca. –99 JK^–1 mol^–1) ions; significant solvation of the released metal ions and the ligand is indicated.     

Rates of reaction of NH2 with N,NO AND NO2

The decay of NH₂ radicals, from 193 nm photolysis of NH₃, was monitored by 597.7 nm laser-induced fluorescence. Room-temperature rate constants of (1.21 ± 0.14) × 10^?10, (1.81 ± 0.12) × 10^?11, and (2.11 ± 0.18) × 10^?11 cm³ molecule^?1 s^?1 were obtained for the reactions of NH₂ with N, NO and NO₂, respectively. The production of NH in the reaction of NH₂ with N was observed by laser-induced fluorescence at 336.1 nm.     

Kinetics of the reaction OH (v = 0) + O3 → HO2 + O2

The rate constant of the reaction OH (v = 0) + O₃

HO₂ + O₂ was measured over the temperature range from 220 to 450°K at total pressures between 2 and 5 torr using ultraviolet fluorescent scattering for the detection of OH radicals. An Arrhenius expression, k₁ = 1.3 × 10^?12 exp(?1900/RT) cm³/sec was obtained and the rate constant for the reaction HO₂ + O₃

OH + 2O₂ was inferred to be less than 0.1 k₁ over the entire temperature interval.     

Synthesis,crystal structure and properties of a copper(II) complex with the tripod ligand tris ( N -methylbenzimidazol-2-ylmethyl)amine and 4-hydroxycinnamate

A five-coordinate copper complex with the tripod ligand tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb) and 4-hydroxycinnamate, with the composition [Cu(Mentb)(4-hydroxycinnamate)](ClO₄)?·?0.5DMF, was synthesized and characterized by means of elemental analyses, electrical conductivities, thermal analyses, IR, and UV. The crystal structure of the copper complex has been determined by single-crystal X-ray diffraction, and shows that the Cu^II atom is bonded to a tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb) ligand and a 4-hydroxycinnamate through four N atoms and one O atom, giving a distorted trigonal-bipyramidal coordination geometry (τ?=?0.78), with approximate C₃ molecular symmetry. Cyclic voltammograms of the copper complex indicate a quasireversible Cu⁺²/Cu⁺ couple. Electron spin resonance data confirm the trigonal–bipyramidal structure and indicate g _∥?<?g _⊥ with a very small value of A _∥ (57?×?10^?4?cm^?1).