New synthetic approach to yttrium hydroxoacetates, structural characterization, and use as a precursor for coated conductors

A novel synthetic approach is given for the preparation of a metal-organic lanthanide sol-gel precursor solution and its application for the production of coated conductors. Besides all other problems concerning the technical process itself, the key to a successful deposition of oxide layers is the choice of the precursor solution and the understanding of the mechanism of deposition. Moreover, the isolation and characterization of the species involved in the reaction is very important. Regarding the complex process occurring during the formation of the surface layer, it is obvious that the best choice should have a compound already containing the final composition of the layer. Two compounds of composition [Y(OAc)3(H2O)2]2 and [Y(OAc)3]2(H2O) were isolated from their precursor solution and characterized by X-ray structural analysis. A short outlook will give an insight into the possible bonding mechanisms of the surface layer. These experiments were made with the mixed metal-oxide system yttrium-stabilized zirconium oxide, which is widely used as a substrate for superconducting oxides. A study of the structure of hydrated yttrium acetates, by single-crystal X-ray diffraction, infrared spectra, and elemental analysis demonstrates that there are two separate structures for hydrated yttrium acetates, which play a role as an intermediate in the building of ceramic oxide layers for coated conductors.     

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Selective 3,3-Rearrangement of Azobenzenes upon Complexation by a Frustrated Lewis Pair

The reaction of the oxygen-bridged frustrated Lewis pairs (FLPs) tBu₂P−O−Si(C₂F₅)₃ ( 1 ) and tBu₂P−O−AlBis₂ ( 2 ) with azobenzene, promoted by UV irradiation, led to a selective complexation of the cis-isomer. The addition product of 2 is stable, while the adduct of 1 isomerizes in solution in an ortho-benzidine-like [3,3]-rearrangement by cleavage of the N−N bond, saturation of the nitrogen atoms with hydrogen atoms and formation of a new bond between two phenyl ortho-carbon atoms. Similar rearrangements take place with different para-substituted azobenzenes (R=Me, OMe, Cl) and di(2-naphthyl)diazene, while ortho-methylated azo compounds do not form adducts with 1 . All adducts were characterized by multinuclear NMR spectroscopy and elemental analyses and the mechanism of the rearrangement was explored by quantum-chemical calculations.     

Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic-ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives

An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC-ITMS). Selecting specific fragment ions within the electron ionization (EI(+)) mass spectra of these oxime derivatives as precursor ions for MS-MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, (E)-2-alkenals, (E,E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI(+) mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.