Aluminum(III) complexes containing O,O chelating ligand

The stoichiometric reactions of trimethylaluminum with 2,6‐(MeOCH₂)₂C₆H₃OH (LH) revealed compounds L₃Al ( 1 ) and L₂AlMe ( 2 ). On the other hand reaction of 1 equiv. of LH with trimethylaluminum did not lead to the formation of complex LAlMe₂ ( 3 ), rather 2 together with Me₃Al were observed as a result of a disproportionation of 3 . Compounds 1 and 2 were characterized by elemental analysis, ¹H and ¹³C NMR spectroscopy and in the case of 1 by X‐ray diffraction. Derivative 2 underwent transmetalation with Ph₃SnOH, giving LSnPh₃ ( 4 ) as the result of a migration of ligand L from the aluminum to the tin atom. The identity of 4 was established by elemental analysis, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and ¹H, ¹¹⁹Sn HMBC experiments. The system 2 and B(C₆F₅)₃ in a 1:1 molar ratio was shown to be active in the polymerization of propylene oxide and ε‐caprolactone. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and conformational study of 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines

A new class of endocyclic enamines, 1,6-disubstituted 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines, was synthesized from 4-piperidone imines by successive subjecting the latter to lithiation with lithium diethylamide, to alkylation with 1-bromo-3-chloropropane, and to intramolecular cyclization. All stages were carried out as a unique process without isolation of the intermediate compounds. A thorough optimization of the process conditions, workup, and product storage was carried out. The conformational study of 1,6-disubstituted 1,2,3,4,5,6,7,8-octahydro-1,6-naphthiridines was performed.     

Chlorokomplexe von Cu2+ und Ni2+ in Dimethylformamid

Zusammenfassung Durch spektrophotometrische Messungen in Dimethylformamid (DMF) werden die Koordinationsformen [CuCl]⁺ und [CuCl₃]^– sowie [NiCl]⁺, [NiCl₃]^– und [NiCl₄]^2– nachgewiesen. Bei Nickel(II)-chlorid und Kupfer(II)-chlorid wird Autokomplexbildung diskutiert. Die Solvate [Cu(DMF)₄] (ClO₄)₂ und [Ni(DMF)₆] (ClO₄)₂ werden isoliert.Im Zuge der Untersuchungen über Chlorokomplexe von Ionen der Übergangsmetalle^{1, 2} in nichtwäßrigen Lösungsmitteln wurden die Spektren der Lösungen von Kupfer(II)- und Nikkel(II)-perchlorat inDMF in Gegenwart verschiedener Mengen Tetraäthylammoniumchlorid aufgenommen.Mit 5 Abbildungen     

Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue

Monoclinic (N₂H₆)₃Zr₂F₁₃·F crystallizes in space group P2₁-C ₂ ² (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,=93.88(1)°,V=658.7(4) ų andZ=2. Two different types of N₂H₆ ²⁺ ions are present. One is involved in strong H-bonds to F^– ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr₂F₁₃ ^5– ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N₂H₂ ²⁺ ions. The Zr₂F₁₃ ^5– ions have very nearly C₂ point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF₈-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N₂H₆)₃Hf₂F₁₃·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N₂H₆ ^– ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.     

Cyclic deformation of aluminium and its alloys

The formation of slip bands is the main mechanism of cyclic deformation in pure Al. Their density, orientation and heights in polycrystalline Al were investigated during cycling. Types, sizes and densities of precipitates are responsible for the mode of cyclic deformation in AlCu4 pure alloy. In technical Al alloys intermetallic phases have detrimental effects on deformation homogeneity and largely govern the fatigue mechanism of the material and especially microcrack initiation.     

The complex scaling method for Dirac resonances

The method of complex scaling, usually used in atomic and molecular resonance calculations, is generalized to the Dirac equation. It is shown that Dirac resonances are associated with nonreal eigenvalues of the scaled Dirac Hamiltonian. The perturbation theory for the resonance parameters is also discussed.     

Einige Gesetzmäßigkeiten der spontanen Umwandlung der Wasserstofform des Montmorillonits in die Aluminium-form

Ohne Zusammenfassung     

Aggregation des menschlichen Serumalbumins unter den Bedingungen der W ärmedenaturierung

Ohne Zusammenfassung     

Rotational contour analysis of the electronic origin band in the emission spectrum of the orthoxylyl radical at 4683 Å

The rotational contour of the 4683 Å emission band of the o-xylyl radical was studied at high resolution. Calculations of the rotational contour of this hybrid band were made in the rigid rotor approximation for various sets of values of the excited state rotational constants and directions of the transition moment μ. Matching of computed and experimental rotational features showed that μ is oriented at +37° or ?37° with respect to the b inertial axis. The nature of the excited states of o-xylyl and the methyl-to-ring interaction are discussed with respect to these two possible assignments