Synthesis and characterization of adducts of dichlorosulphato bis(1,3-propylenediamine)metal(II) complexes with dialkyltin dichlorides

Summary Adducts of dichlorosulphato bis(1,3-propylenediamine)-metal(II) complexes with dialkyltin dichlorides, [R₂Sn(MeCN) ₂]₂[M(NH(CH₂)₃NH)₂(SO₃Cl)₂] (M = Cr, Fe, Co, Ni or Cu; R = Me or n-Bu) have been prepared. The positive shift in the symmetric SO₃ stretch and splitting of the doubly degenerate (E) modes in their i.r. spectra suggest a covalent linkage for the SO₃Cl^– group. The adducts are non-electrolytes; magnetic moments and ligand field data suggest that each SO₃Cl^– group is monodentate, generating an octahedral geometry around the metal ions, except for Ni^II where tetragonal distortion is observed.Author to whom all correspondence should be directed.     

Dimethyl telluride as a ligand: synthesis and physicochemical studies on its complexes with transition metal bis(chlorosulphates) M(SO3Cl)2(M=Cr,Mn, Fe,Co, Ni,Cu)

Summary Dimethyl telluride, Me₂Te, reacts with first row transition metal bis(chlorosulphates), M(SO₃Cl)₂(M=Cr^II, Mn^II, Fe^II, Co^II, Ni^II, Cu^II) in MeCN resulting in the formation of compounds of the type [M(SO₃Cl)₂-(Me₂Te)₂]. These compounds are stable under N₂ but decompose on exposure to moist air. The covalent nature of bonding of the SO₃Cl^– group has been ascertained on the basis of a positive shift in ₁ (A) vibration, splitting of the doubly degenerate (E) modes and low molar conductivity values. The magnetic moments and electronic spectra suggest an octahedral geometry for these compounds (except for the Ni^II complex where a tetragonal distortion is observed) where each SO₃Cl^– group is bonded in a bidentate manner.     

Spectrophotometric Determination of Ruthenium in Solutions of Nitroso and Sulfate Complexes Using Microwave Radiation

It has been shown that ruthenium can be determined in solutions of ammonium nitrosopentachlororuthenate (NH₄)₂[Ru(NO)Cl₅] with nitroso and aquachloro complexes present simultaneously by its reaction with 1,10-phenanthroline and in solutions of sulfate complexes using microwave radiation. It is found by molecular absorption and luminescence studies that the composition of the complex formed corresponds to ruthenium(II) tris-(1,10-phenanthrolinate) {[Ru(Phen)₃]²⁺}. The complexation time is decreased by several tens of times (down to 5 min) compared to conventional heating, and a 100% yield of the complex is achieved. In the presence of HCl, the conversion of nitroso species to aquachloro ruthenium complexes upon microwave irradiation is inefficient. It is found that, compared to [Ru₂OCl₁₀]^4–, [Ru(NO)Cl₅]^2– is more labile in the complexation reactions of ruthenium with 1,10-phenanthroline under microwave irradiation. Regardless of the concentration of H₂SO₄ (1.7–12 M) in the starting solutions, ruthenium sulfate complexes can be converted in a microwave field to more labile chloride complexes.     

Extraction of actinium with di (2-ethylhexyl) phosphoric acid from hydrochloric and nitric acid solutions

The extraction of actinium with HDEHP from Cl^– and NO ₃ ^– systems has been investigated. It was found that extraction of actinium from HCl solutions is much better than from HNO₃ solutions. Stability constants of the actinium complexes Ac(X^–)²⁺, X^–=Cl^– or NO ₃ ^– , were determined. Our results show that actinium formed less stable complexes with Cl^– than with NO ₃ ^– ligands.     

Metal ion complexes of 2-picolinamineN-oxide

Summary A series of cobalt(II), nickel(II) and copper(II) complexes of 2-picolinamineN-oxide, HA, has been prepared. Solids of formula [M(HA)₃](BF₄)₂ (M=cobalt(II) or nickel(II); [Cu(HA)₂]X₂ (X=BF ₄ ^– , NO ₃ ^– ); [Co(HA)₂X₂] (X=Cl^– or Br^–); [Ni(HA)₂Cl₂] and [Cu(HA)X₂] (X=Cl^– or Br^–] have been isolated and characterized by partial elemental analyses, molar conductivities, magnetic susceptibilities, DSC-TGA, and spectral methods. All complexes were found to be monomeric, and their spectral parameters are compared with those of the metal ion complexes ofN-alkyl-2-picolinamineN-oxides, 2-dialkylaminopyridineN-oxides and 2-picolinamine. The cobalt(II) and nickel(II) halide complexes spectrally show a mixture of octahedral and tetrahedral centres.     

Kinetics and mechanism of formation of tetrachloropalladate(II) in the reactions of bis(oxalato)- and bis(malonato) palladate(II) with chloride in acid media

Summary Kinetics of formation of [PdCl₄]^2– from [Pd(ox)₂]^2– and [Pd(mal)₂]^2– has been studies in aqueous acid media in the presence of an excess of chloride ion by stopped-flow spectrophotometry. Both the complexes undergo the transformation in two well separated consecutive steps. In 0.02–0.05 M acid with 0.2 M Cl^–, Pd(AA)^2– dissociates leading to the formation of [Pd(AA)Cl₂]^2– (where AA =ox^2– or mal^2–), which in 0.1–0.6 M acid and 1 M Cl^– forms [PdCl₄]^2– in a relatively slow step. For both steps k_abs=k₀+k₂[H⁺][Cl^–]. Activation parameters corresponding to k₀ and k₂ have been determined. Results indicate that [Pd(mal)₂]^2– is much more labile to substitution than [Pd(ox)₂]^2– and for both the lability is far greater than that of [Pd(bigH)₂]²⁺ and [Pt(ox)₂]^2– reported earlier.     

Adsorption of Cl? ions on electrodeposited rhodium black layer (rhodized electrode) at low concentrations

The adsorption of Cl^– ions on rhodium black layer (rhodized electrodes) was studied by radiotracer technique at low Cl^– ion concentrations (c10^–5 mol dm^–3) in 1 mol dm^–3 H₂SO₄ supporting electrolyte. The specific adsorption of Cl^– ions was treated in terms of partition between solution phase and electrodeposited Rh black layer. The potential dependence of the partition coefficient is determined.     

Trennung einiger Kationen und Anionen mit dem Ringofen

Zusammenfassung Ein systematischer Trennungsgang von Fe(III), Ni(II), Cd(II), Co(II), Cu(II), Al(III), SO₄ ^2–, Cl^– und NO₃ ^– unter Anwendung des Ringofens wird beschrieben.

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Separation of some cations and anions by the ringoven technique

Summary The systematic separation of Fe(III), Ni(II), Cd(II), Co(II), Cu(II), Al(III), SO₄ ^2–, Cl^– und NO₃ ^– by the ringoven-method is described.

     

Coordination compounds derived from transition metal salts and bis(3,5-dimethylpyrazolyl)methane

Summary The preparation of transition metal complexes containing the sterically hindered ligand, bis(3,5-dimethylpyrazolyl)methane (LL) is described. Compounds of formula M(LL)X₂ (M = Co^II, Ni^II or Zn^II and X = Cl^– or Br^–) or M(LL)₂X₂ (M = Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Zn^II or Cd^II and X = ClO ₄ ^– ; M = Co^II, Ni^II, Cu^II or Zn^II and X = NO ₃ ^– ; M = Ni^II or Cu^II and X = Cl^– or Br^–) have been isolated. In addition, an apparently trimeric Cu₃(LL)₄Cl₆ · EtOH compound is reported. For Ni(LL)Cl₂ a five-coordinated chloro-bridged dimer is found. The perchlorato compounds, M(LL)₂(ClO₄)₂, appear to have one bidentate ClO ₄ ^– and one ionic ClO ₄ ^– group. The M(LL)₂ species appears to occur either in octahedral geometry, leaving twocis-positions free, or in a tetrahedral geometry without space for other ligands, and probably also in a five-coordinate geometry with one free ligand position.Structural conclusions are drawn from i.r., far-i.r. and ligand-field spectra, x-ray powder patterns, magnetic susceptibility data, e.s.r. spectra and conductivity data.     

Cobalt(II), nickel(II) and copper(II) complexes of syn-2-picolyl phenyl and syn-2-quinaldyl phenyl ketoximes

Summary The syn-2-picolyl phenyl ketoxime (HL₁) and the syn-2-quinaldyl phenyl ketoxime (HL₂) give [M(HL)LX], [M(HL)₂X₂] and [ML] solid complexes (M=Co, Ni and Cu; X=Cl^–, Br^– and NO ₃ ^– which have been characterized by elemental analysis, room temperature magnetic moments and electronic and i.r. spectral measurements.     

Transition metal ion complexes of theS-methyldithiocarbazate prepared from 2-acetylpyridineN-oxide

Summary Metal ion complexes of theS-methyldithiocarbazate of 2-acetylpyridineN-oxide, HONS, have been prepared and characterised by spectral and physical methods. Preparative ethanolic solutions on reflux yield complexes in which the deprotonated form of the ligand, ONS, is complexedvia itsN-oxide oxygen, azomethine nitrogen, and thione sulphur. Representative stoichiometries are as follows: [M(ONS)₂]X (M=Fe³⁺, and X=ClO ₄ ^– , FeCl ₄ ^– or M=Co³⁺ and X=BF ₄ ^– ) and [M(ONS)X] (M=Co²⁺, Ni²⁺ and Cu²⁺ and X=Cl^–, Br^–). The i.r., electronic, and electron spin resonance spectra of the complexes are compared to analogous complexes of theX-methyldithiocarbazate of 2-acetylpyridine as well as the thiosemicarbazones of 2-acetylpyridineN-oxide.     

Copper(II) complexes of isobutyl methyl ketone semicarbazone

Summary Copper(II) complexes of isobutyl methyl ketone semicarbazone have been prepared and characterised by magnetic moments, i.r., electronic and e.s.r. spectral studies. The complexes were found to have CuL₂X₂ and CuL₂X₂ · 2H₂O compositions. The electronic and e.s.r. spectra suggest a five-coordinated trigonal bipyramidal geometry, for the CuL₂X₂ complexes, (X=Cl^–, Br^–, NO ₃ ^– , and 1/2 SO ₄ ^2– ) and six-coordinate octahedral geometry has been suggested for CuL₂X₂ · 2H₂O (X=Cl^–, Br^–, NO ₃ ^– , SO ₄ ^2– ).     

Reaction of pentaammine(urea-O)cobalt(III) cation with chlorine and hypochlorous acid in aqueous solution

Summary The Co(NH₃)₅[OC(NH₂)₂]³⁺ cation in aqueous acid reacts with chlorine and hypochlorous acid, with two sequential steps observed in each case. Rate constants for both steps show a first-order dependence on [oxidant], with k₁/k₂ always <20, but varying with the choice of reactant and acid. Rate constants with Cl₂ as reactant are faster than with HOCl, possibly related to preferential attack by Cl⁺ compared with OCl^– on the bound urea. Competition by ions (HSO ₄ ^– , Cl^– or NO ₃ ^– ) measured by product analysis of reactions conducted in 1 M acid produced competition ratios R (R=[CoX]/[CoOH₂][X]) which are similar to values determined with a range of leaving groups previously, indicating a mechanistic constancy. No formation of Co(NH₃)₅Cl²⁺ was observed in reactions conducted in H₂SO₄ or HNO₃, implying that free Cl^– is not generated at the reaction site and captured by the metal ion. Electronic and vibrational spectra of the intermediate formed in the two stage reaction is indicative of a change from an O-bound to an N-bound ligand in forming that intermediate, although it cannot be a simple isomerization due to the dependence on [oxidant]. A possible mechanism is discussed.     

Transition metal chemistry of oxime-containing ligands,part XI. Copper(II) complexes of syn-phenyl-2-pyridylketoxime and syn-methyl-2-pyridylketoxime

Summary Some copper(II) complexes of the types: Cu(HPPK)-(PPK)X, Cu(HMPK)(MPK)X (where HPPK = syn-phenyl-2-pyridylketoxime, HMPK = syn-methyl-2-pyridylketoxime and X = Cl^–, Br^–, I^–, NO₃ ^–, SCN^– or SeCN^–) Cu(HPPK)₂SO₄ 3 H₂O and Cu(HMPK)₂SO₄ · 3 H₂O were synthesized and characterized by analysis, magnetic susceptibility, e.s.r., reflectance and i.r. spectral measurements. The spectral data suggest that Cu(HPPK)(PPK)X and Cu(HMPK)(MPK)X containcis square-coplanar [Cu(HPPK)(PPK)]⁺ and [Cu(HMPK)(MPK)]⁺ units respectively, linked by weakly coordinated anions, giving infinite polymeric highly distorted octahedral chain structures, whereas Cu(HPPK)₂SO₄ · 3H₂O and Cu(HMPK)₂SO₄ · 3 H₂O have acis distorted octahedral structure containing two ligand molecules of ketoxime and a bidentate sulphate group. The polycrystalline e.s.r. spectra suggest a distorted octahedral stereochemistry for the Cu^II ion involving a ground-state. By using e.s.r. and reflectance spectral data, the orbital reduction parameters, k₁₁ and k₁ were calculated and interpreted in terms of molecular orbital coefficients.     

Influence of Anions on Electrochemical Properties of Polypyrrole-Modified Electrodes

The influence of anions ClO₄ ^–, NO₃ ^–, Cl^–, SO₄ ^2–, and DDS^– (dodecyl sulfate) on the cyclic voltammetric response of polypyrrole-modified electrodes is studied. The change in the film composition is examined by electron probe microanalysis. It is established that essential changes in the shape of voltammograms take place during cycling if the anions are not sufficiently freely mobile in the polymer film and insertion of cations from the solution is necessary to guarantee electroneutrality of the system. Some differences between the mobility of Cl^– ions and ClO₄ ^– or NO₃ ^– ions are in good agreement with the results of semi-empirical quantum chemical calculations showing that the interaction of Cl^– and Br^– ions with pyrrole oligomers is stronger than that of NO₃ ^– or ClO₄ ^– ions. Nevertheless, it is established that the peak current determined from voltammograms increases linearly with the increase of the scan rate with very high correlation coefficient. It means that it is possible to describe the behavior of ClO₄ ^–, NO₃ ^– and Cl^– ions in the framework of the model of free ions. The redox behavior of the PPy films doped with anions of low mobility such as SO₄ ^2– and DDS^– depends essentially on the nature of cations in the test solution. It is found that the mobility of cations increases in the row Li⁺ < Na⁺ < K⁺ < Cs⁺. The mobility of DDS^– ions in the PPy in ethanolic solution is significantly higher and their electrochemical properties are quite similar to PPy|Cl or NO₃ ^– film in aqueous solution.     

Titration von Sulfid mit einer sulfidionensensitiven Elektrode

Zusammenfassung Eine Methode zur potentiometrischen Titration von Sulfid mit Natriumplumbat(II)lösung an einer sulfidsensitiven Membranelektrode wird beschrieben. Sie eignet sich zur Bestimmung von 10^–4% Sulfid in Gegenwart von Cl^–, Br^–, J^–, SCN^–, SO₃ ^2–, S₂O₃ ^2–

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Titration of sulphide with a sulphide-ion sensitive electrode

A method is described for the titration of sulphide with sodium plumbate(II) solution using a sulphide-sensitive electrode. The method is suitable for the determination of 10^–4% of sulphide in the presence of Cl^–, Br^–, J^–, SCN^–, SO₃ ^2–, S₂O₃ ^2–.

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Wir danken Herrn Dr. K. Obst für wertvolle Hinweise und Diskussionen.     

Complexes of Some 3d-Metal Salts with N,N-Dimethylhydrazide of 4-Nitrobenzoic Acid

The [M(HL)₂(H₂O)₂]X₂ complexes were synthesized (M = Mn(II), Co(II), Ni(II), Cu(II), Zn; X = CH₃COO^–, Cl^–, BF₄ ^–) that incorporate bidentately coordinated molecules of N,N-dimethylhydrazide of 4-nitrobenzoic acid (HL). The latter molecules chelate the metal atom through the carbonyl O atom and the N atom of dimethylamino group. The square-planar complexes of Cu and Ni with deprotonated form of a ligand with composition ML₂ were also isolated. The synthesized complexes were studied by IR, electronic and EPR spectroscopies, and by cyclic voltammetry.     

Studies on ruthenium(III), rhodium(III) and iridium(III) complexes of indazoles

Summary New complexes of the general formula M(L)₃Cl₃ and M(5-AInz)₂Cl₃ · n H₂O (where M = Ru^III, Rh^III and Ir^III; L = indazole and 5-nitroindazole; n=1–2) have been synthesized and characterised by elemental analysis, molar conductance, magnetic susceptibility and i.r. and electronic spectral measurements. All the complexes are covalent and apparently have an octahedral geometry. The ligands are monocoordinated through the pyrrole nitrogen. From the far i.r. spectra amer configuration has been assigned to the indazole and 5-nitroindazole complexes.     

Complexing of cerium(IV) with nitrilotriacetic acid in the presence of sulfate and nitrate ions

Conclusions The authors have made a spectrophotometric investigation of the composition of the complexes formed in the system Ce(IV)-nitrilotriacetic acid in 1 M (NH₄)₂SO₄ and 1 M NH₄NO₃ solutions and have calculated the instability constants of CeX⁺ and CeX ₂ ^2– complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1448–1451, July, 1976.