The preparation,phase relationships,and Eu-151 Mössbauer spectroscopy of europium tungsten bronzes and related phases

Crystal chemistry and phase relations for the bronze-forming region of the EuWO system have been investigated. A bronze Eu_xWO₃ is stable up to 1000°C when x ? 0.125 and in the region 0.085 ? x ? 0.125 the symmetry is cubic. A tetragonal bronze exists at x = 0.05, and an orthorhombic bronze with a structure closely related to the orthorhombic form of WO₃ exists below x = 0.01. Mössbauer spectra at room temperature and at 80 K indicate that in all these phases the europium is highly ionized as Eu(III) with no electron localization to give (EuII) even at low values for x. The decomposition products of the bronzes have been established, and the Mössbauer parameters for the highly nonstoichiometric tungstates Eu_xWO₄ were determined. Both Eu(II) and Eu(III) resonances were obtained, and a cation vacancy model for Eu_xWO₄ was found to fit the data best. In conformity with the foregoing data, a sample of composition “Eu₂W₂O₇” was found not be be a pyrochlore but to comprise a mixture of Eu₆WO₁₂, Eu_xWO₄, and W. The phase relationships for the europium bronze system Eu_xWO₃ are compared with those of other ionic bronzes Na_xWO₃, Li_xWO₃, and Al_xWO₃.     

Rearrangement thermique des α-ceto, α-cyano epoxydes en dioxoles : Etude du mecanisme de la reaction

The thermolysis of α-cyano α-keto epoxides to give dioxoles is a new rearrangement. The reactivity of the epoxides is dependent upon the nature of the substituents on the epoxide ring, and solvent polarity. When the reaction is carried in the presence of benzaldehyde, a 1,3 cycloadduct is obtained. These results are in good agreement with a carbonyl ylide intermediate.     

Structural requirements in chiral diphosphine-rhodium complexes. VIII. Asymmetric hydrogenation of N-acetyldehydroamino acids with rhodium(I) complexes containing chiral carbocyclic analogues of DIOP.

Z--acetamidocinnamic acid was hydrogenated with neutral diphosphine-rhodium(I) complexes containing trans-1,2-bis(diphenylphosphinomethyl) cycloalkanes to give N-acetylphenylalanine: 86 % e.e.-(R) [(1R,2R)-cyclobutane]; 63 % e.e.-(R) [(1R,2R)-cyclopentane]; 35 % e.e.-(S) [(1S,2S)-cyclohexane]; and 82 % e.e.-(R) [(2R,3R)-DIOP]. Similarly, -acetamidoacrylic acid was hydrogenated to give N-acetylalanine: 72 % e.e.-(R) [(1R,2R)-cyclobutane]; 72 % e.e.-(R) [(1R,2R)-cyclopentane]; 40 % e.e.-(S) [(1S,2S)-cyclohexane]; and 73 % e.e.-(R) [(2R,3R)-DIOP].     

Thermal addition of dibenzoylacetylene to cycloheptatriene and the photo-rearrangement of the thermal adduct

The reaction of cycloheptatriene (CHT) with dibenzoylacetylene (DBA), in refluxing toluene gave a mixture of products consisting of 6,7-dibenzoyltricyclo[3.2.2.0^2.4]nona-6,8-diene 6 and 3,4-dibenzoylbicyclo [3.2.2]nona-2,6,8-triene 7. Neat heating of a mixture of CHT and DBA around 95–100° gave besides, 6 and 7, small amounts of two dimers of DBA. Photolysis of 6 in benzene solution gave a lactonic, rearrangement product. 25. The structures of the various products have been established and reasonable mechanisms for their formation have been suggested.     

Lanthanon (III) Complexes of Bifunctional Tridentate and Tetradentate Schiff Bases

Reactions of isopropoxides of praseodymium, neodymium and samarium with bifunctional tridentate and tetradentate schiff bases (i.e. salicylidene-O-aminophenol and bis-salicylaldehyde ethylenediamine) have been carried out in benzene in different stoichiometric ratios resulting in the formation of products with the formula M(OPrⁱ)(C₁₁H₉NO₂), M(C₁₃H₉NO₂)(C₁₃H₁₀NO₂). M₂(C₁₃H₉NO₂) M(OPrⁱ)(C₁₅H₁₄N₂O₂), M(C₁₆H₁₄N₂O₂)(C₁₆H₁₅N₂O₂) and M₂(C₁₆H₁₄N₂O₂)₃ (where M stands for Pr, Nd and Sm). The products were found to be yellow to orange solids soluble in benzene and alcohol. The absorption spectra of these complexes were also recorded in methanol.     

Thiapyrylium salts (review)

The literature data touching upon the synthesis of thiapyrylium salts and the stability of the thiapyrylium cation as compared with its isoelectronic analogs, as well as the nucleophilic, oxidation, anion-exchange, and other reactions of the salts with substituted and unsubstituted thiapyrylium cations are examined in this review.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Influence of mobility of medium on dynamics of metallotropy in tin-containing 2-R-oxyphenoxyls

The rate of intramolecular migration of the triphenylstannyl group in 3,6-ditert-butyl-2(triphenylstannyl) oxyphenoxyl decreases with increasing viscosity of the medium. A linear relationship _ex=·_c is observed between the characteristic time of stannotropy _ex and the correlation time for reorientational motions of the radical _c within a range of temperature variation no greater than 30°C. The parameter depends on the medium; this is explained by the possibility of complexation of the radical with the solvent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 781–786, April, 1990.     

Chemical Synthesis,Proton NMR. Parameters,Hydrogen- and Calcium-Ion. Complexation of L-γ-Carboxyglutamyl-L-γ-carboxyglutamic Acid and D-γ-Carboxyglutamyl-L-leucine

The purpose of this communication is to describe the preparation and some properties of the first two synthetic peptides containing D - and L -γ-carboxyglutamic acid. Use was made of N-protected γ,γ′-di-t-butyl-γ-carboxyglutamic acids (D , L , and DL ) described earlier [1 a]. Preliminary ¹H-NMR. data (360 MHz) indicate a restricted rotation of the Gla side chain in the free amino acid as well as in the C-terminal Gla of Gla-Gla in H₂O solution at acid pH. The proton dissociation from Gla and Gla-Gla was studied by potentiometric titration and NMR. methods. The pH titration in the presence of Ca²⁺ ions shows that Gla-Gla has a much higher association constant for this cation than Gla. It is almost as great as that of prothrombin (pCa²⁺ = 3.2 vs. 3.5).