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41.
42.
Both single crystals of VCl3(THF)3 as well as isotypic cocrystals of the composition MCl3(THF)3, M=Ti/V 1/3, undergo a topotactic reversible phase transition to a hitherto unknown low-temperature modification. The close relationship between this new structure and the room-temperature phase determined by Cottonet al. is discussed from the molecular and the intermolecular point of view: Both modifications are built up by conformationally very similar molecules which change their arrangement during the phase transition. Lattice energy calculations confirm that these two alternative arrangements correspond to minima of almost the same packing energy.Dedicated to Professor Dr. G. E. Herberich on the occasion of his 60th birthday. 相似文献
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44.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemical communications (Cambridge, England)》2005,(40):5115-5117
Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters. 相似文献
45.
Matthias Bauer Christoph Gastl Christoph Köppl Guido Kickelbick Helmut Bertagnolli 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):567-581
Summary. The molecular structure of the transition metal alkoxide Zr(OnBu)4 in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy.
Zr(OnBu)4 dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand.
In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the
structural models is given in terms of possible alternatives and errors within the EXAFS analysis. 相似文献
46.
The objective of this work was to evaluate the use of composite mass spectral (CMS) data from pyrolysis gas chromatography/mass spectrometry (PY–GC/MS) for lignocellulosic materials. Various forages, by-products and fiber fractions derived from them were examined as CMS by PY–GC/MS. The PY–GC/MS system consisted of a heated platinum filament, a capillary gas chromatograph and an ion trap detector (ITD) mass spectrometer operated under electron impact conditions. Mass spectra were then composited in several ways by summing all the mass spectra acquired within retention times corresponding to major product classes. CMS data were entered in a dedicated library and compared using the ITD library editor software. The usefulness of such a simple procedure for studies related to lignocellulose analysis, such as forage recognition, development of analytical methods and digestibility/maturity correlation, is discussed. 相似文献
47.
Cyanide Bridged Coordination Polymers from cis‐ or trans‐[Ru(tBuNC)4(CN)2] and MnCl2: About the Influence of Different Topologies on the Magnetic Properties of Materials The reaction of cis‐ or trans‐[Ru(tBuNC)4(CN)2] with MnCl2 as an additional transition metal fragment yields the one dimensional coordination polymers {cis‐[Ru(CN)2(tBuNC)4] MnCl2}n, ( 1 ), and {trans‐[Ru(CN)2(tBuNC)4]MnCl2}n, ( 2 ), with a different arrangement of the metal centers caused by the different stereochemistry of the starting compounds. The variation of the Ru‐C‐N‐Mn geometry nevertheless leads to significant differences in the magnetic properties of 1 and 2 . The coordination polymer derived from trans‐[Ru(tBuNC)4(CN)2] shows a more efficient antiferromagnetic intrachain interaction between the manganese centers compared to the cis‐derivative. 相似文献
48.
The order in thin films of a combined liquid crystalline polymer is studied by X-ray reflection. Films of thicknesses of less than 200 nm on float glass are investigated as a function of temperature. The polymer with mesogenic groups in the main and side-chains exhibits smectic and cholesteric mesophases. Measurements in the smectic phases show a Bragg peak and smectic layers are oriented parallel to the substrate. The sample is thus macroscopically ordered by the influence of substrate and free surface. The film surface is very smooth after spincoating; surface roughness is typically 0.8 nm. First annealing of samples leads to a significant roughening of the free surface; roughness increases to 2.1 nm. Order as a function of film thickness depends on the interaction of the polymer with the substrate and free surface. These interactions give rise to a typical correlation length of perturbations in smectic ordering. 相似文献
49.
50.
InIII-Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)ammonium-cis-di(nitrito-O,O')phthalocyaninato(2–)indate(III) [In(Cl)Pc2?] reacts with (nBu4N)NO2 in acetone yielding green-blue (nBu4N)cis[In(NO2)2Pc2?], which crystallizes in the monoclinic space group P21/n (No. 14). Both nitrite anions are coordinated as chelating nitrito-O,O'(NO2) ligands to InIII in cis-geometry. Consequently InIII is octa-coordinated within a distorted “quadratic” antiprism and directed towards the Pc2?-ligand. One of the NO2 ligands has equivalent N? O bonds similar to free nitrite, while the other has asymmetric N? O bonds. Both (In,O,N,O) rings are approximately planar with a dihedral angle of 80°. The Pc2? ligand is distorted in an asymmetrically convex manner. Partially overlapping pairs of Pc2? ligands related by an inversion center form double layers, which are separated by layers containing the (nBu4N)+ cations. The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc3?/Pc2? (?0.94 V) < InI/InIII (-0.78 V) < Pc2?/Pc? (0.64 V). The UV-VIS-NIR spectra and vibrational spectra are discussed. 相似文献