Synthesis of new dinuclear dicopper(II) and dinickel(II) complexes. The kinetics of catechol oxidase and electrochemistry of a dicopper(II) complex

A new dinuclear ligand L, ethylene[OO-bis-salicylidene--diketone] bearing two symmetrical coordination sites was synthesized by the condensation of salicylaldehyde and acetylacetone, L, with 1,2-dibromoethane under reflux. The ligand L in a 1:1 ratio was treated with CuCl₂ and NiCl₂ to yield the complexes, tetrachloro bis[OO-bis- salicylidene--diketone copper(II)] and bis[OO-bis-salicylidene--diketone nickel(II)] chloride. The complexes were subsequently characterized by spectroscopic techniques, elemental analysis, i.r., ¹H-n.m.r., ¹³C-n.m.r., u.v.–vis., e.p.r. spectroscopy, and conductance measurements. The conductance measurements in DMF reveal that the Cu^II complex is covalent while the Ni^II complex is ionic and the spectral data support the Cu^II complex to be distorted octahedral whereas the Ni^II complex has square-planar geometry. The dioxygen binding was studied spectrophotometrically by the oxidation of tetrachloro bis[OO-bis-salicylidene--diketone copper(II)] with pyrocatechol in the presence of oxygen. The kinetic experiments were performed with the copper complex in DMF by monitoring the increase in absorbance over time at pH 8.0 in the presence of pyrocatechol at 25 °C. The kinetic parameters V_max and K_M were determined on the Michaelis–Menten Approach. Redox behavior of the dinuclear copper(II) complex was investigated by cyclic voltammetry in the presence of O₂ with the pyrocatechol (substrate) and also without the substrate. The large difference in potentials E⁰ is indicative of reversible oxygen binding of the complex and distinct catalytic activity.     

Spectrophotometric investigation of nickel(II) chloro complexes in alcoholic solutions

Summary A spectrophotometric study of Ni^II chloro complexes in the u.v.-vis. region was carried out at 25 °C and constant ionic strength of 1 mol dm^–3. A matrix rank treatment method was used to identify two successive mononuclear complexes, NiCl⁺ and NiCl₂, in the three alcohols studied viz. MeOH, EtOH and i-PrOH. The best values for the apparent overall stability constants, _j , were calculated using a program based on the least-squares method. The log ₁ and log ₂ values in MeOH, EtOH and i-PrOH are 1.3 and 1.2, 1.7 and 1.8, and 1.9 and 2.2, respectively. The stability increases directly with the mol. wt. of the solvent, or decreases as a linear function of the permittivity of the pure solvent. The electronic spectra and the formation curves of the two complexes in MeOH solutions were calculated.     

Octahedral and tetrahedral configuration changes of nickel(II) chloro complexes from spectrophotometric studies in aprotic solvents

Four NiII chloro complexes were identified spectrophotometrically in aprotic media such as DMSO, DMF and propylene carbonate for the first time. An original multiwavelength numerical treatment, based on a Marquardt method, results in the determination of the individual electronic spectra of the mononuclear chloro complexes and of their stability constants, the values of which indicate the presence of rather weak complexes in DMSO and DMF, much stronger in the less solvating propylene carbonate solvent. The overall stability constants calculated for the NiII chloro complexes are: 1=52, 2=140, 3=160, 4=210 in DMSO, 1=60, 2=110, 3=900, 4=15000 in DMF, 1=1.6×109, 2=6.4×1015, 3=2.7×1021, 4= 5.1×1026 in PC.The solvent effect is discussed in terms of the quantitative results obtained from this spectrophotometric study and reveals that the stability of the complexes is an inverse function of the donor properties of the solvent. This result illustrates the general behavior of complex formation in dipolar aprotic solvents, i.e. the substitution of one solvent molecule in the inner coordination sphere by the ligand is easier if the solvation strength of the solvent is lower. The solvent effect is also described in terms of the variation of shifts of the calculated absorption maxima for the individual electronic spectra of the chloro complexes. This result is used to identify clearly at which step of coordination the octahedral configuration of the nickel ion changes to the tetrahedral configuration, by comparison with the well-known structural properties of these complexes in the solid state.     

Synthesis and magnetic properties of copper(II) bis(phenylsulphinyl)ethane complexes

Summary Two Cu^II complexes, [Cu₂(-L)Cl₄·H₂O (1) and Cu₂(-L)Cl₄ (2) [-L and -L = meso- and rac-PhS(O)(CH₂)₂S(O)Ph, respectively], were synthesized and characterized by elemental analysis, i.r. spectra and molar conductances. In each case, the Cu^II ion bonds to the 557-01 moiety through oxygen, and may be bridged by the ligand (-L or -L). From magnetic moment measurements at room temperature and variable temperature magnetic susceptibilities, we suggest that complexes (1) and (2) exhibit weak ferromagnetic behaviour.     

Electron Delocalization in 3d Complexes Caused by Dimethylurea Checked by Positron Annihilation

The rate constants, k _CR, of ortho- into para-positronium conversion reactions promoted by paramagnetic 3d complexes are linearly correlated with the electron delocalization, , of unpaired metal electrons caused by ligands, being the ratio between the inter-electronic repulsion parameters in complexes and in the free gaseous ions. By applying a procedure previously described the values of Mn^II, Co^II, Ni^II complexes with dimethylurea were deduced from the mentioned correlations and compared with those of complexes with urea obtained both by the method of Ps reactions here applied and that based on UV-Vis absorption spectroscopy.     

Inclusion Complexes of Cyclodextrins with Tetrakis(4-carboxyphenyl)porphyrin and Tetrakis(4-sulfonatophenyl)porphyrin in Aqueous Solutions

In neutral and alkaline solutions, tetrakis(4-carboxyphenyl)porphyrin (TCPP) and tetrakis(4-sulfonatophenyl)porphyrin (TSPP) form 1:1 and 2:1 host–guest inclusion complexes with -cyclodextrin (-CD), -cyclodextrin (-CD), and 6-deoxy-6-diethylamino--CD (DEA--CD), except for DEA--CD in alkaline solution. On the other hand, TCPP and TSPP form only 1:1 inclusion complexes with 6-deoxy-6-dihexylamino--CD (DHA--CD). The limited solubilities of DEA--CD in alkaline solution and DHA--CD are likely responsible for no observation of the 2:1 inclusion complex containing DEA--CD in alkaline solution and that containing DHA--CD. The equilibrium constants (Ks) of TCPP and TSPP for the formation of the inclusion complexes have been estimated from the absorption and/or fluorescence intensity changes in neutral and alkaline solutions. The K₂ values, which are the equilibrium constants for the formation of the 2:1 host–guest inclusion complex from the 1:1 inclusion complex, are about one tenth the corresponding K₁ values, except for the -CD–TSPP system in alkaline solution. In neutral solution, where DEA--CD and DHA--CD are in protonated forms, the electrostatic force operates between DEA--CD (DHA--CD) and TCPP (TSPP), leading to the greater K values than those in alkaline solution, where DEA--CD and DHA--CD exist as neutral species.     

Synthesis and properties of some chromium(III) β-diketonate complexes

Summary Equimolar quantities of CrCl₃ · 3THF and-diketones, -dkH, react to yield CrCl₂(-dk) · 2THF and CrCl₂(-dk) · THF complexes in coordinating and noncoordinating solvents respectively. For 1 : 2 and 1 : 3 molar ratios of reactants, derivatives of general formulae CrCl(-dk)₂ and Cr(-dk)₃ (where-dkH = acerylacetrrnc, benzoylacetonc and dibenzoylmethane) have been isolated. All complexes have been characterized by elemental analysis, molecular weights and by i.r. spectra.     

Controlled-potential coulometric studies on fluoride and sulphate complexes of neptunium (VI)

Fluoride and sulphate complexing of Np(VI) has been studied by controlled-potential coulometry at a constant ionic strength. The values of ₁ ^* and ₂ ^* for fluoride complexes were found to be 9.4 and 8.9, respectively, at an ionic strength =0.5. At an ionic strength =1.0, ₁ ^* and ₂ ^* obtained were 6.6 and 10.5, respectively. Sulphate complexing of Np(VI) was studied only at an ionic strength =0.5. The value of ₁ ^* obtained was 5.6.     

Preparation and structure of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 3-amino-5-(α/β)pyridyl-1, 2, 4-triazoles

Summary Complexes of bidentate 3-amino-5-()-pyridyl-1,2,4-triazole (L¹) and 3-amino-5-()-pyridyl-1, 2, 4-triazole (L²) of composition [ML¹Cl₂·H₂O], [ML²Cl₂·H₂O], [ML ₃ ^2/1 Cl₂] and [ML ₃ ^2/2 Cl₂] [M=Co^II, Ni^II, Cu^II, M=Zn^II] have been prepared and characterized by elemental analyses, i.r., u.v./visible, e.s.r. spectra, magnetic moments and molar conductances.     

Prediction of Stability Constants for Cr(III) and Cr(II) Complexes

Regression analysis was used to derive equations for estimaing thermodynamic stability constants for complexes of Cr²⁺ (log^° ₁[Cr²⁺L] = 0.53log^° _n [H _n L]) and Cr³⁺ (log^° ₁[Cr³⁺L] = 0.88log^° _n [H _n L]) from the known protonation constants of H _n L ligands and for determining stability constants of Cr²⁺ and Cr³⁺ complexes from the available stability constants of Cu²⁺ complexes (log^° ₁[Cr²⁺L] = 0.76log^° ₁[Cu²⁺L] and log^° ₁[Cr²⁺L] = 0.60log^° ₁[Cr³⁺L], respectively). Parameters of the Panteleon–Ecka equation for calculating stability constants of Cr²⁺ complexes ( = 0.57) and Cr³⁺ complexes ( = 0.69) with two and three bidentate ligands were also determined. The ratio of logarithmic stability constants for complexes with the same metals but with different metal ionic charges was found to be approximately equal to the ratio of charges on the central ions. The stability constant of Cr(II) sulfate complex was calculated.     

Naphthyl-(2-pyridylmethylene)amine complexes of silver(I) and ruthenium(II): synthesis,spectral studies and electrochemical behaviour

Pyridine-2-carboxaldehyde reacts with /-naphthylamine to give /-naphthyl-(2-pyridylmethylene)amine [-L (1), -L (2)]. L belongs to the unsymmetric diimine (—N=C—C=N—) family which can form five–membered chelate rings with metal ions. {donor centers are abbreviated as N[N(Py)] and N [N(nap)]} [Ag(L)₂]⁺ complexes were prepared and characterized by spectroscopic data. The reaction between L and RuCl₃ in boiling EtOH yielded green and blue–green compounds of composition RuCl₂(L)₂. I.r., u.v.–vis. and ¹H-n.m.r. data determined the stereochemistry of the complexes as trans-cis-cis (green) and cis-trans-cis (blue–green) according to the sequence of the coordination pair of Cl, N [N(Py)] and N [N(nap)]. Upon treatment of Ag(L)₂ ⁺ with Ru(bpy)₂Cl₂ in alcoholic suspension the ternary complexes, [Ru(bpy)₂(L)](ClO₄)₂, were isolated and characterized by spectroscopic data. [Ru(bpy)(L)₂](ClO₄)₂ complexes were synthesized similarly from ctc-Ru(L)₂Cl₂ and 2,2-bipyridine (bpy) in the presence of AgNO₃ and NaClO₄. These complexes show well-defined m.l.c.t transitions in the visible region. The sterochemistry of the complexes was established by ¹H-n.m.r. data. Cyclic voltammetry shows a high potential Ru^III/Ru^II couple and follows the order: [Ru(bpy)(L)₂]²⁺ > [Ru(bpy)₂(L)]²⁺ > Ru(-L)₂Cl₂ > Ru(-L)₂Cl₂.     

Rotaxane Type Complexation Behavior of Cyclodextrins with Zinc (II) Tetraphenylporphyrin-Viologen Linked Compounds

The complexation behavior of zinc (II) tetraphenylporphyrin-viologen covalently linkedcompounds by a polymethylene chain (ZnPC_nV²⁺; n = 4–9) withtri-O-methyl--cyclodextrin (TM--CD) was investigated by meansof ¹H NMR and UV/Vis absorption spectrometry in acetonitrile-water (1:1, v/v).The ¹H NMR spectra indicated that ZnPC_nV²⁺ existed as a mixture ofa dimer and a monomer at high concentration (>1 × 10^-3 M). The dimerwas degraded to the monomer upon complexation with TM--CD involving theformation of 1:1 and 1:2 (ZnPC_nV²⁺: TM--CD) complexes, whichwas observed by UV/Vis spectrometry. Furthermore, ¹H NMR spectra exhibitedthat there are at least two types of structures for these complexes, one is a fastexchanging complex, and another is a slow exchanging one. A slow exchanging complexcould be assigned as a rotaxane type structure in which the methylene chain moiety ofZnPC_nV²⁺ penetrated into the cavity of TM--CD. Discrete formationconstants for these complexes were evaluated. The values were little affected by the spacermethylene chain length (n 7).     

Synthesis,spectroscopy and thermal properties of the nickel(II), palladium(II) and copper(II) complexes of bis(aminoalkyl)-oxamides (=LH2) including the crystal structure of Cu2L(NO3)2

Summary The synthesis of the Ni^II, Pd^II and Cu^II complexes of N, N-bis(aminoalkyl)oxamides (LH₂) is described and structures are proposed on the basis of their physical and spectroscopic properties. With Ni^II and Pd^II only one complex is formed with general formula NiL or PdL, characterised by coordination through two deprotonated amide N-atoms and two terminal NH₂ groups. With Cu^II it proved possible to obtain three structurally different compounds, depending on the pH, with general formulae Cu(LH₂)X₂, Cu₂(L)X₂ and CuL in which X=Cl, Br or NO₃. The structure of [Cu₂(C₈O₂N₄H₁₆](NO₃)₂ was solved by means ofx-ray diffraction; Mr=451.33, monoclinic, space group P2₁/n, a=9.503(4), b=7.614(1), c=10.407(3) Å, =98.43(3)°, V=744.3(7)ų, Z=2, Dx=1.202 g cm^–3, =1.33 cm^–1, (MoK)=0.71073 Å, F(000)=520, room temperature, R=0.043, wR=0.047 for 1080 observed [I>-3(I)] not systematically absent reflections out of 1423 measurements and 137 variables. The compound has a conformational chair/boat disorder with 82% in the more stable chair form.     

Trans-cis Photoisomerization of 1-Methyl-4-(4′-hydroxystyryl)pyridinium in inclusion complexes ofβ-cyclodextrin and its derivatives

The effects of -cyclodextrin (-CyD), heptakis(2,6-di-O-methyl)--cyclodextrin (DMCyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TMCyD) ontrans-cis photoisomerization of 1-ethyl-4-(4-hydroxystyryl)pyridinium (POH) have been studied in aqueous solutions. The ratio of [cis]/[trans] for POH in the photostationary state at pH 8.54 was remarkably reduced by the presence of CyD or DMCyD. The reduction of the [cis]/[trans] ratio in the photostationary state was explained in terms of the shift of the equilibrium of POH ₊ ^trans PO _trans + H^– toward PO _trans formation. The binding constants of CyD and DMCyD for PO _trans were 2.00- and 1.36-fold larger than those for POH ₊ ^trans , respectively. The binding constants of TMCyD for both species are much smaller than those of CyD and DMCyD. This result indicates that PO _trans , which has a betain structure, forms stable complexes with CyD and DMCyD with its hydrophobic parts inside and the charged parts outside the CyD cavities.     

Violurato complexes of nickel(II). Formation equilibria. Deprotonation equilibria of the coordinated ligands and related stereochemical changes

Summary The formation equilibria of nickel(II) violurato-complexes in water and dimethylsulphoxide-water (8020) as well as deprotonation of the coordinated ligands and related stereochemical changes are reported. The stability constants of the Ni²⁺-H₂V^– complexes log₁=5.06, Iog₂=9.38, log₃=12.98 as well as the acidity constants of the [Ni(H₂V)₃]^– complex, log_j1= 8.37, log_j2=15.76, log_j3=22.37 are determined at 25 °C and 0.1M NaClO₄. A new violurato-complex of Ni²⁺, Na₄[Ni(HV)₃]5H₂O, is isolated and characterized.     

Crystal structure of monohydrate and anhydrous β-alaninium tetrafluoroantimonates(III)

Novel complexes of Sb(III) fluorides with cation of -aminopropionic acid (-alanine), (NH₃(CH₂)₂COOH)SbF₄ H₂O (I) and (NH₃(CH₂)₂COOH)SbF₄ (II), are synthesized and their crystal structures are determined. Crystals I and II are monoclinic with a = 12.1580(5) , b = 7.4167(4) , c = 10.1540(5) , = 108.222(2)°, Z = 4, space group P2₁/c for (I) and a = 10.483(1) , b = 7.5906(8) , c = 9.4237(9) , = 90.548(2)°, Z = 4, space group P2₁/c for (II). Structures I and II are formed by -alaninium cations (C₃H₈NO₂)⁺ and complex anions [SbF₄] _n ^n– with polymer chain structure. Complex I also contains crystallization water molecules. In the structures of complexes I and II, the -alaninium cations have different conformation, the torsion angles C(1)C(2)C(3)N in these complexes are 174.5° and 77.0°C, respectively.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 243–247.Original Russian Text Copyright © 2005 by Udovenko, Zemnukhova, Kovaleva, Davidovich.     

Spectroscopic and thermodynamic studies on solvatochromic nickel(II) complexes

Summary The solvatochromic and thermochromic behaviour of a series of mixed Ni(II) complexes with unsubstituted and substituted -diketones and diamines in the solvents 1,2-dichloroethane (DCE), acetonitrile (An), acetone (AC),n-butanol (n-BuOH), formamide (FA), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (PY) has been studied and characterized on the basis of electronic spectra. Spectrophotometric methods have been used to evaluate equilibrium constants and their enthalpic and entropic terms for the formation of Ni(-dik)(diam)L ⁺ and Ni(-dik)(diam)L ₂ ⁺ . Increasing donor strength of the donor-solvents (L) and (or) increasing electronwithdrawing parameters of the substituents at the -diketone and the diamine ligands lead to increasing formation constants, paralleled by relative increase in the stability of the five-coordinated species Ni(-dik)(diam)L ⁺. The results are discussed in terms of the extended donor-acceptor concept.On leave of absence from the Faculty of Education, Ain Schams University, Roxy, Cairo, Egypt     

ESR study of NiIII complexes with nitrosonaphthols and dithio acids

Mixed-ligand Ni^III complexes with -nitroso--naphthol, -nitroso--naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square Ni^IIL₂ complexes to more stable octahedral Ni^IIIL₂L and Ni^IIILL₂ complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.Translted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1515, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5050)     

Potentiometric Investigation of Fluoride Complexes of Zirconium(IV) and Hafnium(IV) in 1 <Emphasis Type="Italic">M</Emphasis> (H,Na)ClO<Subscript>4</Subscript> Medium Using a Fluoride Ion Selective Electrode

The stability constants of zirconium(IV) and hafnium(IV) fluoride complexes in 1 M (H,Na)ClO₄ medium were measured potentiometrically at 293 K for the first time using a fluoride ion selective electrode (F-ISE). This technique has been recommended by IUPAC as the best tool for studying fluoride complexes. A number of precautions were taken to ensure the stabilization of zirconium or hafnium in 1 M (H,Na)ClO₄ medium and to prevent the formation of polynuclear hydroxo complexes. The formation of only mononuclear complexes was indicated. The average log values of the overall stability constants of zirconium(IV)-fluoride complexes, ₁, ₂, ₃ and ₄ were computed by varying the concentration of metal ion and were found to be 8.49 ± 0.11, 15.76 ± 0.15, 21.57 ± 0.10, and 26.68 ± 0.16, respectively, whereas the corresponding values for hafnium(IV)-fluoride complexes were 8.22 ± 0.06, 15.48 ± 0.15, 21.76 ± 0.14, and 27.42 ± 0.15, respectively. The thermodynamic stability constant, ₁, calculated for these complexes follows the same trend as expected from the linear correlation based on the Brown Sylva Ellies (BSE) model for metal-fluoride complexes provided the effective charge on Zr is taken as +4.1 instead of the formal charge of +4. Without considering this adjustment of formal charge, an attempt has also been made to explain the trend in ₁ values of group(IV) metal-fluoride complexes based on electronegativity values. A good linear correlation was obtained that could explain the ability of these group(IV) ions to form different fluoride complexes with varying number of fluoride ions.     

Electrode kinetics and thermodynamic study of complexes of palladium(II) at D.M.E.

Polarographic study of Pd(II) reveals that it reduces quasireversibly at d.m.e. in 0.2M-pyridine+0.1N-HCl medium. Kinetic parameters of Pd(II) in various concentrations of -resorcyclic acid were calculated usingGellings method and thus the effect of concentration of -resorcyclic acid on the kinetics of the reduction of Pd(II) has been explained.DeFord/Hume graphical extrapolation method and the mathematical method ofMihailov have been employed for the evaluation of overall formation constants of the complexes formed with -resorcyclic acid. The logarithmic values of overall formation constants ₁, ₂ and ₃ obtained by the two methods are 7.47, 8.60, 9.66 (DeFord andHume Method) and 7.44, 8.64, 9.66 (Mihailov Method) at 298 K. Thermodynamic parameters of these complexes are reported.

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Elektrodenkinetik und thermodynamische Untersuchungen an Pd(II)-Komplexen mittels polarographie

Zusammenfassung Pd(II) zeigt eine quasireversible Reduktion in 0,2M-Pyridin/0,1N-HCl. Kinetische Parameter wurden mittels der Methode vonGelling ermittelt und damit der Effekt verschiedener -Resorcylsäurekonzentrationen erklärt. Bildungskonstanten der entsperechenden Komplexe wurden nachDeFord/Hume und nachMihailov ermittelt. Die logarithmischen Werte der Gesamtbildungskonstanten ₁, ₂ und ₃ bei 298 K betragen nach derDe Ford/Hume-Methode 7,47, 8,60 und 9,66, nach derMihailov-Methode 7,44. 8,64 und 9,66. Die thermodynamischen Parameter der Komplexbildung werden angegeben.