Extraktiv-photometrische Bestimmung von Rhodium unter Verwendung von Diphenylselenoxid

Zusammenfassung Innerhalb der substituierten Selenoxide eignet sich Diphenylselenoxid, das in salzsaurer Lösung die Verbindung RhCl₃·OSe(C₆H₅) bildet, zur extraktiv-photometrischen Bestimmung des Rhodiums besonders neben Co²⁺, Ni²⁺ und Fe³⁺.

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Summary Among the substituted selenium oxides, diphenylselenium oxide, that in hydrochloric acid solution yields the compound RhCl₃·OSe(C₆H₅)₂, is especially suitable for the extractive-photometric determination of rhodium, particularly in the presence of Co²⁺, Ni²⁺ and Fe³⁺.

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Résumé Dans le cadre des oxydes de sélénium substitués, le diphényloxyde de sélénium qui forme le composé RhCl₃·OSe(C₆H₅) en solution chlorhydrique se prête au dosage photométrique par extraction du rhodium, en particulier en présence de Co²⁺, Ni²⁺ et Fe³⁺.

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Der Deutschen Forschungsgemeinsehaft und dem Fonds der chemischen Industrie danken wir für die Förderung unserer Arbeit durch Sachbeihilfen.     

Pyrrolothienopyrazines: Synthèse de la pyrrolo[1,2-a]thieno[3,2-e]pyrazine et de la pyrrolo[1,2-a]thieno[2,3-e]pyrazine

The synthesis of pyrrolo[1,2-α]thieno[3,2-e]pyrazine and pyrrolo[1,2-α]-thieno[2,3-e]pyrazine is described. These syntheses could be achieved by intramolecular cyclization of 2- (and 3-) (1-pyrrolyl)-3- (and -2)-thienyl-amines obtained by hydrolysis of carbamates or by cleavage of the corresponding ureas. An original way giving better results was also studied via a Curtius rearrangement by reaction between the azide and aldehyde groupings. The synthesis of 2- (and -3)-2-formyl-1-pyrrolyl)-2- (and -3)-thenoylazide is described.     

Padé approximants and their application to scattering from fluid media

In this work, a numerical method for modeling the scattered acoustic pressure from fluid occlusions is described. The method is based on the asymptotic series expansion of the pressure expressed in terms of sound speed contrast between the host medium and entrained fluid occlusions. Pade? approximants are used to extend the applicability of the result for larger values of sound speed contrast. For scattering from a circular cylinder, an improvement in convergence between the exact and numerical solutions is demonstrated. In the case of scattering from an inhomogeneous medium, a numerical solution with reduced order of Pade? approximants is presented.     

A finite element,filtered eddy-viscosity method for the Navier–Stokes equations with large Reynolds number

The direct numerical simulation of the Navier–Stokes system in turbulent regimes is a formidable task due to the disparate scales that have to be resolved. Turbulence modeling attempts to mitigate this situation by somehow accounting for the effects of small-scale behavior on that at large-scales, without explicitly resolving the small scales. One such approach is to add viscosity to the problem; the Smagorinsky and Ladyzhenskaya models and other eddy-viscosity models are examples of this approach. Unfortunately, this approach usually results in over-dampening at the large scales, i.e., large-scale structures are unphysically smeared out. To overcome this fault of simple eddy-viscosity modeling, filtered eddy-viscosity methods that add artificial viscosity only to the high-frequency modes were developed in the context of spectral methods. We apply the filtered eddy-viscosity idea to finite element methods based on hierarchical basis functions. We prove the existence and uniqueness of the finite element approximation and its convergence to solutions of the Navier–Stokes system; we also derive error estimates for finite element approximations.     

Surface charging of layered double hydroxides during dynamic interactions of anions at the interfaces

In this research, we investigated the effect of dynamic anion adsorption/exchange on the surface charging property of Mg(2)AlClLDH and Mg(2)AlCO(3)LDH particles that show the average zeta potential of 41 and 34 mV in the as-prepared suspension, respectively. The addition of NaCl up to 3x10(-3) M in the suspension does not obviously affect the zeta potential of both LDHs, which can be attributed to the less affinity of Cl(-) to LDH. The introduction of Na(2)CO(3) severely reduces the zeta potential at the CO(3)(2-) concentration higher than 1x10(-4) M, and to the negative value in both LDH systems at ca. 2x10(-3) M, which is presumably resulted from the exchange and the re-orientation of CO(3)(2-) in a tilt/vertical style on the surface. All four organic anions (dodecyl sulfate, folate, citrate and polyacrylate) also significantly affect the zeta potential of the LDH particles. At the lower concentrations of organic anionic groups (<1x10(-4) M), the zeta potential was slightly affected, i.e. limited exchange/adsorption. However, the concentration increasing to some point suddenly decreases and reverses the zeta potential of the LDH particles, which is presumably caused by the hydrophobic interactions that bind the hydrophobic hydrocarbon chains (especially in dodecyl sulfate) into the micelle-like bilayer bunches on the LDH surface. In addition, the effect of pH in 5.5-11.0 on the LDH particle surface charging is mainly reflected through the conversion of CO(3)(2-) to HCO(3)(-)/H(2)CO(3) when pH decreases from ca. 11 to 6, with limited contribution from protonation/deprotonation and exchange/adsorption.     

Nouveaux trioxophosphetanes generateurs d'oxygene singulet a basse temperature

We have prepared phosphite ozonides $\text{1b}$–$\text{3b}$ which are efficient and clean singlet oxygene generators at low temperature.     

Unexpected Disproportionation of Tetramethylethylenediamine-Supported Perchlorodisilane Cl(3)SiSiCl(3)

The addition compound Cl(3)SiSiCl(3)·TMEDA was formed quantitatively by treatment of Cl(3)SiSiCl(3) with tetramethylethylenediamine (TMEDA) in pentane at room temperature. The crystal structure of Cl(3)SiSiCl(3)·TMEDA displays one tetrahedrally and one octahedrally bonded Si atom (monoclinic, P2(1)/n). (29)Si CP/MAS NMR spectroscopy confirms this structure. Density functional theory (DFT) calculations have shown that the structure of the meridional isomer of Cl(3)SiSiCl(3)·TMEDA is 6.3 kcal lower in energy than that of facial coordinate species. Dissolving of Cl(3)SiSiCl(3)·TMEDA in CH(2)Cl(2) resulted in an immediate reaction by which oligochlorosilanes Si(n)Cl(2n) (n = 4, 6, 8, 10; precipitate) and the Cl(-)-complexed dianions [Si(n)Cl(2n+2)](2-) (n = 6, 8, 10, 12; CH(2)Cl(2) extract) were formed. The constitutions of these compounds were confirmed by MALDI mass spectrometry. Additionally, single crystals of [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(6)Cl(14)] and [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(8)Cl(18)] were obtained from the CH(2)Cl(2) extract. We found that Cl(3)SiSiCl(3)·TMEDA reacts with MeCl, forming MeSiCl(3) and the products that had been formed in the reaction of Cl(3)SiSiCl(3)·TMEDA with CH(2)Cl(2). X-ray structure analysis indicates that the structures of [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(6)Cl(14)] (monoclinic, P2(1)/n) and [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(8)Cl(18)] (monoclinic, P2(1)/n) contain dianions adopting an "inverse sandwich" structure with inverse polarity and [Me(3)NCH(2)CH(2)NMe(2)](+) as countercations. Single crystals of SiCl(4)·TMEDA (monoclinic, Cc) could be isolated by thermolysis reaction of Cl(3)SiSiCl(3)·TMEDA (50 °C) in tetrahydrofuran (THF).     

Synthesis of aminopyridines and aminopyridones by cobalt-catalyzed [2+2+2] cycloadditions involving yne-ynamides: scope, limitations, and mechanistic insights

An in-depth study of the cobalt-catalyzed [2+2+2] cycloaddition between yne-ynamides and nitriles to afford aminopyridines has been carried out. About 30 nitriles exhibiting a broad range of steric demand and electronic properties have been evaluated, some of which open new perspectives in metal-catalyzed arene formation. In particular, the use of [CpCo(CO)(dmfu)] (dmfu=dimethyl fumarate) as a precatalyst made possible the incorporation of electron-deficient nitriles into the pyridine core. Modification of the substitution pattern at the yne-ynamide allows the regioselectivity to be switched toward 3- or 4-aminopyridines. Application of this synthetic methodology to the construction of the aminopyridone framework using a yne-ynamide and an isocyanate was also briefly examined. DFT computations suggest that 3-aminopyridines are formed by formal [4+2] cycloaddition between the nitrile and the intermediate cobaltacyclopentadiene, whereas 4-aminopyridines arise from an insertion pathway.     

Highly diastereoselective ionic/radical domino reactions: single electron transfer induced cyclization of bis-sulfoxides

SET oxidation of bis-sulfinyl anions has enabled the uses of bis-sulfinyl radical as a synthetic equivalent of chiral acyl and methylene radicals involved in tandem reactions leading to the enantioselective construction of various carbo- and heterocyclic derivatives.