Determination of submicrogram quantities of osmium by catalysis

Summary The osmium catalysis of the Ce(IV)-As(III) reaction is made the basis of a general method for the determination of 0.001 to 0.2g Os per milliliter. The rate of reaction can be determined photometrically or potentiometrically.Osmium is isolated by extraction of the tetroxide with chloroform or carbon tetrachloride, and returned to aqueous medium by shaking with arsenious acid-sulfuric acid solution which is then treated with eeric ammonium sulfate to effect the final determination. Ruthenium which is also a strong positive catalyst for the Ce(IV)-As(III) reaction will be kept in reduced form and will not be extracted by the organic solvents if the solution of Os(VIII) and Ru(VIII) is treated with a slight excess of ferrous iron and then with nitric acid to make its concentration about 5M. Iodine, the other strong catalyst for the reaction, can be inactivated by silver ion. Osmium recoveries of 90 per cent or better can be obtained from solutions containing as little as 0.0002 p. p. m. Os.The kinetics of the osmium catalyzed ceric-arsenious reaction has been investigated. The rate is independent of the Ce(IV) concentration but is a function of the As(III) concentration. The slow step in the catalyzed reaction is therefore the reduction of Os(VIII) by As(III).

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Zusammenfassung Die Katalyse der Reaktion zwischen Ce(IV) und As(III) durch Osmium dient als Grundlage der Bestimmung des letzteren in Lösungen, die 0,001 bis 0,2g Osmium im Milliliter enthalten. Die Reaktionsgeschwindigkeit kann photometrisch oder potentiometrisch bestimmt werden.Das Osmium wird als Tetroxyd mit Chloroform oder Tetrachlorkohlenstoff extrahiert. Beim Schütteln dieses Extraktes mit schwefelsaurer Lösung von arseniger Säure geht Osmiumtetroxyd in die wässerige Phase über und wird zum Zweck der quantitativen Bestimmung mit Ceriammoniumsulfat behandelt. Ruthenium, das die Reaktion beeinflußt, wird in der ursprünglichen Lösung zurückgehalten, indem man diese vor Extraktion mit dem organischen Lösungsmittel mit Ferroammoniumsulfat und Salpetersäure behandelt. Jodid, das ebenfalls die Reaktion stark beschleunigt, wird durch Zugabe von Silbersulfat unschädlich gemacht. Aus 210¹⁰ verdünnten Lösungen kann auf diese Weise das Osmium zu 90% und mehr wiedergefunden werden.Die Kinetik der katalysierten Reaktion wurde untersucht. Die Reaktionsgeschwindigkeit ist eine Funktion der As(III)-Konzentration und unabhängig von der Ce(IV)-Konzentration. Die langsame Teilreaktion ist daher die Reduktion von Os(VIII) durch As(III).

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Résumé La catalyse par l'osmium de la réaction Ce(IV)-As(III) est à la base d'une méthode générale pour le dosage de 0,001 à 0,2g d'osmium par ml. La vitesse de réaction peut être déterminée photométriquement ou potentiométriquement. L'osmium est isolé en extrayant le tétroxyde par le chloroforme ou le tétrachlorure de carbone et remis en milieu aqueux par agitation avec la solution acide arsénieux-acide sulfurique qui est alors traitée par le sulfate cérique ammoniacal pour produire le dosage final. Le ruthénium qui est aussi un catalyseur fortement positif pour la réaction Ce(IV)-As(III) sera maintenu sous la forme réduite et ne sera pas extrait par les dissolvants organiques si la solution Os(VIII) et Ru(VIII) est traitée par un léger excès de fer ferreux puis avec l'acide nitrique pour rendre sa concentration environ 5 M. L'iode, autre catalyseur positif puissant pour la réaction peut être rendu inactif par l'ion argent. A partir de solutions ne contenant que 0,0002 p. p. m. d'osmium on peut en récupérer mieux que 90%.La cinétique de la réaction cérium-arsenic catalysée par l'osmium a été soumise à l'expérience. La vitesse est indépendante de la concentration en Ce(IV) mais c'est une fonction de la concentration en As(III). Le palier lent de la réaction catalysée est par conséquent la réduction de Os(VIII) par As(III).

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From a portion of the Ph. D. thesis ofR. D. Sauerbrunn, 1952.     

Dicyclopentadienyl-niobium(iii) and -niobium(iv) complexes

The reduction of (η-C₅H₅)₂NbCl₂ (I) under various conditions gives the dimer (η-C₅H₅)₄Nb₂Cl₃ (II) containing niobium(III) and niobium(IV). Reaction of II with AgClO₄ gives [(η-C₅H₅)₄Nb₂Cl₂]⁺ ClO₄^- (III). FeCl₃ and (C₆F₅)₂ TlBr displace I from II to give (η-C₅H₅)₂Nb(μ-Cl)(μ-X)MY₂, where MFe, XYCl(IV) and MTl, XBr, YC₆F₅ (V). Reactions of I with metal halides MXY₂ give (η-C₅H₅)₂ClNb(μ-Cl)MXY₂ where XYCl, MAl (VI), Fe (VII), Tl (VIII) and XBr, YC₆F₅, MTl (IX). The chemical behaviour of all these compounds is described.     

Amperometric titration of cerium(iii) with ferricyanide

Milligram and larger quantities of cerous cerium may be determined accurately and precisely, even in the presence of large amounts of ceric salts, by amperometric titration in 3 to 4M potassium carbonate solution with potassium ferricyanide. A rotating platinum microelectrode held at the potential of the saturated calomel electrode is recommended.     

A simple thermometric technique for reaction-rate determination of inorganic species, based on the iodide-catalysed cerium(IV)-arsenic(III) reaction

A very simple reaction-rate thermometric technique is used for determination of iodide (5-20 ng ml ), based on its catalytic action on the cerium(IV)-arsenic(III) reaction, and for determination of mercury(II) (1.5-10 ng ml ) and silver(I) (2-10 ng ml ), based on their inhibitory effect on this reaction. The reaction is followed by measuring the rate of temperature increase. The method suffers from very few interferences and is applied to determination of iodide in biological and inorganic samples, and Hg(II) and Ag(I) in pharmaceutical products.     

Determination of traces of ruthenium by addition of cerium(IV) and atomic absorption spectrometry

The sensitivity of the determination of ruthenium by flame atomic absorption spectrometry is increased 60 times by adding 1 × 10^?2 M cerium(IV). Calibration is linear over the range of 0.05–5 μg ml^?1 ruthenium. A method applicable to nitrosylruthenium complexes is described. The increased sensitivity results from formation of ruthenium tetroxide.     

Determination of sub-nanogram quantities of ruthenium by flameless atomic absorption spectrometry

Flameless atomic absorption spectrometry has been applied to the determination of subnanogram quantities of ruthenium in a variety of matrices encountered in the solidification of nuclear waste. Detection limits ranged to below 10^?10 g, depending on the sample matrix. Most matrix effects could be eliminated by proper selection of atomizer temperature program, allowing the use of a single set of standards in 0.1 N HCl. The one exception was the calcined solid matrix, where a fusion and extraction were used to dissolve the ruthenium and separate it from matrix constituents.     

Synthesis of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bis-ketoiminate using microwave heating

Preparation of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bisketoiminate (Pd(i-acac)₂) under microwave irradiation using different synthetic conditions, both in the solid-phase and in solution, was studied with precise control of parameters. In the solid-phase systems, the preparation of the target product was hindered. The efficiency of the microwave heating increased when liquid phases of the reagent mixtures were used. For Pd(i-acac)₂, the highest yield was achieved under elevated temperature of the process, with the reaction time decreasing to several minutes. A laboratory procedure for the microwave synthesis of ruthenium(iii) and rhodium(iii) tris-acetylacetonates and palladium(ii) bis-ketoiminate in aqueous solutions was developed, which allowed us to obtain them in 85, 55, and 80% yields, respectively. These yields are higher than those reported in the literature, with the process becoming considerably less time consuming and laborious.     

Determination of cerium(III) and cerium(IV) in nanodisperse ceria by chemical methods

Percentages of different valence cerium species have been determined in powdery samples, redispersible compositions, and aqueous sols of nanodisperse ceria prepared from cerium(IV) and cerium(III) salts by various methods with or without organic stabilizers. Cerium(III) is shown to be virtually absent in nearly all of the CeO₂ samples studied. Organic stabilizers are shown to be capable of reducing cerium(IV) in aqueous CeO₂ sols.     

Mangana(iii/iv)electro-catalyzed C(sp3)–H azidation

Manganaelectro-catalyzed azidation of otherwise inert C(sp³)–H bonds was accomplished using most user-friendly sodium azide as the nitrogen-source. The operationally simple, resource-economic C–H azidation strategy was characterized by mild reaction conditions, no directing group, traceless electrons as the sole redox-reagent, Earth-abundant manganese as the catalyst, high functional-group compatibility and high chemoselectivity, setting the stage for late-stage azidation of bioactive compounds. Detailed mechanistic studies by experiment, spectrophotometry and cyclic voltammetry provided strong support for metal-catalyzed aliphatic radical formation, along with subsequent azidyl radical transfer within a manganese(iii/iv) manifold.

The merger of manganese-catalyzed C–H functionalization with electrosynthesis enabled C(sp³)–H azidation devoid of chemical oxidants or photochemical irradiation. Detailed mechanistic studies are supportive of a manganese(iii/iv) electrocatalysis.     

Deaminative meta-C–H alkylation by ruthenium(ii) catalysis

Precise structural modifications of amino acids are of importance to tune biological properties or modify therapeutical capabilities relevant to drug discovery. Herein, we report a ruthenium-catalyzed meta-C–H deaminative alkylation with easily accessible amino acid-derived Katritzky pyridinium salts. Likewise, remote C–H benzylations were accomplished with high levels of chemoselectivity and remarkable functional group tolerance. The meta-C–H activation approach combined with our deaminative strategy represents a rare example of selectively converting C(sp³)–N bonds into C(sp³)–C(sp²) bonds.

Precise structural modifications of amino acids are of importance to tune biological properties or modify therapeutical capabilities relevant to drug discovery.     

Determination of ultratrace amounts of ruthenium(III) by the delayed autocatalytic reaction using citric acid.

A method for determination of ultratrace amounts (ppq levels) of ruthenium(III) was developed using a copper(II)-phthalocyanine-3,4',4",4"'-tetrasulfonic sodium salt (Cu-PTS) as an indicator in a potassium bromate autocatalytic reaction system. A satisfactory calibration curve of ruthenium(III) ion was obtained by the time measurement in the concentration range of 1 x 10(-13) M to 5 x 10(-12) M with the relative standard deviation (RSD) of 2.8% (n=5). The determination limits (3sigma) were 3.30 x 10(-14) M (3.34 ppq).     

Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tellurium(IV) by cerium(IV)

The reaction is zero order in cerium(IV), fractional order in tellurium(IV) and first oder in ruthenium(III). While the ionic strength has no effect, the rate increases with increasing [H⁺], and decreases with increasing [HSO ₄ ^– ]. H and S are 54.4 kJ mol^–1 and –60.3 JK^–1 mol^–1, respectively. A suitable mechanism is proposed.

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(IV), (IV) (III). , [H⁺] [HSO ₄ ^– ]. H S 54,4 ^–1 –60,3 ·^–1·^–1, . .

     

Spektrophotometrische untersuchung der ternaren systeme ruthenium(iii) - zitrat - nitrosonaphthol

Reactions of ruthenium(III) with nitrosonaphthols were studied in weakly acidic media using various spectrophotometric methods. Mixtures of complexes are usually obtained; in citratebuffered medium the complexes I : I and I :3 are formed. Both nitrosonaphthols can be applied for detection of ruthenium(III) in weakly acidic media.     

Nano-sized manganese oxide: a proposed catalyst for water oxidation in the reaction of some manganese complexes and cerium(iv) ammonium nitrate

According to UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy, nano-sized manganese oxides are proposed as active catalysts for water oxidation in the reaction of some manganese complexes and cerium(iv) ammonium nitrate.     

Kinetics of water oxidation with cerium(IV) compounds catalyzed by a tetranuclear ruthenium complex

The kinetics and mechanism of water oxidation with cerium(IV) compounds catalyzed by a tetranuclear ruthenium complex containing two polyoxotungstate ligands are reported. Four water molecules are oxidized via an eight-electron process to form two oxygen molecules.     

High-turnover supramolecular catalysis by a protected ruthenium(II) complex in aqueous solution

The design of a supramolecular catalyst capable of high-turnover catalysis is reported. A ruthenium(II) catalyst is incorporated into a water-soluble supramolecular assembly, imparting the ability to catalyze allyl alcohol isomerization. The catalyst is protected from decomposition by sequestration inside the host but retains its catalytic activity with scope governed by confinement within the host. This host-guest complex is a uniquely active supramolecular catalyst, capable of >1000 turnovers.     

Kinetochromic spectrophotometry-III Determination of fluoride by catalysis of the zirconimn-Methylthymol blue reaction

The determination of 0.5-4.75 mug of fluoride ion by its catalytic action upon the slow reaction between Methylthymol Blue and zirconium(IV) in aqueous solution is described. Calibration curves obtained after 60 min under optimal conditions are smooth, and yield an effective molar absorptivity of 3.23 x 10(4) 1.mole(-1)mm(-1) at 586 nm. There is considerably less cationic interference than in the alizarin complexan-cerium(III) or lanthanum procedure, but more serious anionic interference is encountered when phosphate, arsenate and, to a lesser extent, sulphate ions are present in the sample solution.     

Kinetochromic spectrophotometry-II Determination of sulphate by catalysis of the zirconium-methylthymol blue reaction

A direct spectrophotometric method is proposed for the determination of sulphate, based on its ability to catalyse the slow reaction between Methylthymol Blue and zirconium in slightly aged solution. The procedure is operated in the same way as a normal spectrophotometric method but with stricter control of timing. The interference of 100-fold excesses of 40 other ions was studied. Of these, Ce(III), Sr, Fe(III), Th, Sn(II), U(V), Mn(II), Sb(III), Se(IV), Bi(III), Te(IV), SO(3)(2-), F(-), PO(4)(3-), AsO(4)(3-), S(2-), tartrate, oxalate and citrate interfered. Cationic interferences may be removed by cation-exchange. The interference of equimolar ratios of arsenate, fluoride and phosphate may be removed by preliminary treatment with magnesium oxide. Sulphate may be determined in the range 0.1-2.4 ppm by the recommended procedure with a net molar absorptivity of 2.0 x 10(4) at 586 nm. The colour development time is 60 min.