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11.
Fe/Mn/K catalysts derived from support of the anionic carbonyl, [Fe2Mn(CO)12]– on silica were compared with catalysts prepared by aqueous impregnation methods, and found to be more selective for production of C2–C4 olefins. Addition of K had little effect, whereas variations in reaction conditions altered selectivity owing to secondary reactions of the alkene products.
Fe/Mn/K, , [Fe2Mn(CO)12]–, , , , C2–C4. , , .相似文献
12.
Halochromic Molecules. Synthesis and Acidobasic Properties of 3′-substituted 6,11-dihydrospiro[[1]benzopyrano[4,3-b]indol-6,9′?9′9′H-xanthenes] We have synthesized a series of 3′-substituted 6,11-ihydrospiro[6H-chromeno[4,3-b]indol–6,9′?9′H-xanthenes] and one of their respective aza analogues. 1H-MR data as well as the fragmentation in the mass spectra of starting and final products supported the postulated structures. With acid, the spiro compounds form ring-opened intensely coloured xanthylium salts. UV/VIS spectra of these salts are listed and discussed. The ?pH* curves in buffered MeOH/H2O solutions and the pK* values are determined. The title compounds could possibly be used in ‘pressure sensitive papers’. 相似文献
13.
Most p-block metal amides irreversibly react with metal alkoxides when subjected to alcohols, making reversible transformations with OH-substrates a challenging task. Herein, we describe how the combination of a Lewis acidic square-planar-coordinated aluminum(iii) center with metal–ligand cooperativity leverages unconventional reactivity toward protic substrates. Calix[4]pyrrolato aluminate performs OH-bond activation of primary, secondary, and tertiary aliphatic and aromatic alcohols, which can be fully reversed under reduced pressure. The products exhibit a new form of metal–ligand cooperative amphoterism and undergo counterintuitive substitution reactions of a polar covalent Al–O bond by a dative Al–N bond. A comprehensive mechanistic picture of all processes is buttressed by isolation of intermediates, spectroscopy, and computation. This study delineates how structural constraints can invert thermodynamics for seemingly simple addition reactions and invert common trends in bond energies.The combination of structural constraint and metal–ligand cooperativity in calix[4]pyrrolato aluminate inverts common trends of bond energies and enables reversible OH-bond activation. 相似文献
14.
N.E. Schore B.E. La Belle M.J. Knudsen H. Hope X-J. Xu 《Journal of organometallic chemistry》1984,272(3):435-446
Dicobalt octacarbonyl is shown to react with acetylene and carbon monoxide under mild conditions in dimethoxyethane or benzene to produce, in low yields, bicyclo[3.3.0]octa-3,7-diene-2,6-dione, benzoquinone, and the cyclopentadienone-derived products 3a,4,7,7a-tetrahydro-2,7-methanoindene-1,10-dione, 1-indanone, tetracyclo[5.5.2.02,608,12]tetradeca-4,10,13-triene-3,9-dione, and tetracyclo[5.5.2.02,608,12]tetradeca-4,9,13-triene-3,11-dione. Possible mechanisms for the formation of these products are discussed. 相似文献
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17.
This paper presents a 3D topology optimization approach for designing shell structures with a porous or void interior. It is shown that the resulting structures are significantly more robust towards load perturbations than completely solid structures optimized under the same condi-tions. The study indicates that the potential benefit of using porous structures is higher for lower total volume fractions. Compared to earlier work dealing with 2D topology opti-mization, we found several new effects in 3D problems. Most notably, the opportunity for designing closed shells signifi-cantly improves the performance of porous structures due to the sandwich effect. Furthermore, the paper introduces improved filter boundary conditions to ensure a completely uniform coating thickness at the design domain boundary. 相似文献
18.
Dr. Debangshu Chaudhuri Dr. Eva Sigmund Annemarie Meyer Lisa Röck Philippe Klemm Sebastian Lautenschlager Agnes Schmid Shane R. Yost Prof. Dr. Troy Van Voorhis Dr. Sebastian Bange Prof. Dr. Sigurd Höger Prof. Dr. John M. Lupton 《Angewandte Chemie (International ed. in English)》2013,52(50):13449-13452
19.
Poly(ethylene glycol) (PEG) hydrogels have been used to encapsulate fluorescently labeled molecules in order to detect a variety
of analytes. The hydrogels are designed with a mesh size that will retain the sensing elements while allowing for efficient
diffusion of small analytes. Some sensing assays, however, require a conformational change or binding of large macromolecules,
which may be sterically prohibited in a dense polymer matrix. A process of hydrogel microporation has been developed to create
cavities within PEG microspheres to contain the assay components in solution. This arrangement provides improved motility
for large sensing elements, while limiting leaching and increasing sensor lifetime. Three hydrogel compositions, 100% PEG,
50% PEG, and microporated 100% PEG, were used to create pH-sensitive microspheres that were tested for response time and stability.
In order to assess motility, a second, more complex sensor, namely a FITC-dextran/TRITC-Con A glucose-specific assay was encapsulated
within the microspheres. 相似文献
20.
Shira D. Halperin Hope Fan Stanley Chang Dr. Rainer E. Martin Prof. Robert Britton 《Angewandte Chemie (International ed. in English)》2014,53(18):4690-4693
Fluorination reactions are essential to modern medicinal chemistry, thus providing a means to block site‐selective metabolic degradation of drugs and access radiotracers for positron emission tomography imaging. Despite current sophistication in fluorination reagents and processes, the fluorination of unactivated C? H bonds remains a significant challenge. Reported herein is a convenient and economic process for direct fluorination of unactivated C? H bonds that exploits the hydrogen abstracting ability of a decatungstate photocatalyst in combination with the mild fluorine atom transfer reagent N‐fluorobenzenesulfonimide. This operationally straightforward reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acid derivatives. 相似文献