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81.
A Boron‐Fluorinated Tris(pyrazolyl)borate Ligand (FTp*) and Its Mono‐ and Dinuclear Copper Complexes [Cu(FTp*)2] and [Cu2(FTp*)2]: Synthesis,Structures, and DFT Calculations
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Dr. Timo Augenstein Franziska Dorner Kevin Reiter Hanna E. Wagner Dr. Delphine Garnier Prof. Dr. Wim Klopper Prof. Dr. Frank Breher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7935-7943
Reaction of [Si(3,5‐Me2pz)4] ( 1 ) with [Cu(MeCN)4][BF4] ( 2 ) gave the mono‐ and dinuclear copper complexes [Cu2(FTp*)2] ( 3 ) and [Cu(FTp*)2] ( 4 ). Both complexes contain the so‐far unprecedented boron‐fluorinated FTp* ligand ([FB(3,5‐Me2pz)3]? with pz=pyrazolyl) originating from 1 , acting as a pyrazolyl transfer reagent, and the [BF4]? counter anion of 2 , serving as the source of the {BF} entity. The solid‐state structures as well as the NMR and EPR spectroscopic characteristics of the complexes were elaborated. Pulsed gradient spin echo (PGSE) experiments revealed that 3 retains (almost entirely) its dimeric structure in benzene, whereas dimer cleavage and formation of acetonitrile adducts, presumably [Cu(FTp*)(MeCN)], is observed in acetonitrile. The short Cu???Cu distance of 269.16 pm in the solid‐state is predicted by DFT calculations to be dictated by dispersion interactions between all atoms in the complex (the Cu?Cu dispersion contribution itself is only very small). As revealed by cyclic voltammetry studies, 3 shows an irreversible (almost quasi‐reversible at higher scan rates) oxidation process centred at Epa=?0.23 V (E01/2=?0.27 V) (vs. Fc/Fc+). Oxidation reactions on a preparative scale with one equivalent of the ferrocenium salt [Fc][BF4] (very slow reaction) or air (fast reaction) furnished blue crystals of the mononuclear copper(II) complex [Cu(FTp*)2] ( 4 ). As expected for a Jahn–Teller‐active system, the coordination sphere around copper(II) is strongly distorted towards a stretched octahedron, in accordance with EPR spectroscopic findings. 相似文献
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Dr. Matthieu Fonvielle Dr. Inés Li de La Sierra‐Gallay Dr. Afaf H. El‐Sagheer Maxime Lecerf Delphine Patin Dr. Dénia Mellal Dr. Claudine Mayer Dr. Didier Blanot Dr. Nittaya Gale Dr. Tom Brown Dr. Herman van Tilbeurgh Dr. Mélanie Ethève‐Quelquejeu Dr. Michel Arthur 《Angewandte Chemie (International ed. in English)》2013,52(28):7278-7281
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An adaptive (Lagrangian) boundary element approach is proposed for the general three‐dimensional simulation of confined free‐surface Stokes flow. The method is stable as it includes remeshing capabilities of the deforming free surface and thus can handle large deformations. A simple algorithm is developed for mesh refinement of the deforming free‐surface mesh. Smooth transition between large and small elements is achieved without significant degradation of the aspect ratio of the elements in the mesh. Several flow problems are presented to illustrate the utility of the approach, particularly as encountered in polymer processing and rheology. These problems illustrate the transient nature of the flow during the processes of extrusion and thermoforming, the elongation of a fluid sample in an extensional rheometer, and the coating of a sphere. Surface tension effects are also explored. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
84.
A facile access to a wide range of original saturated N-heterocyclic ureas is described using, as a key step, a Michael-type reaction involving isocyanates or amines on a piperidine framework possessing an α,β-unsaturated ester functionality. 相似文献
85.
Pd/Cu-catalyzed one-pot reaction of 1-trimethylsilyl-2-arylalkynes with propargylic chlorides in the presence of TBAF is described. The present new procedure is applicable to a wide range of silylated arylalkynes with both electron-withdrawing and electron-donating substituents. Functionalized allenynes can thus be obtained in good yields without prior deprotection of the alkynes. 相似文献
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Modulation of Relaxivity,Suspension Stability,and Biodistribution of Dendronized Iron Oxide Nanoparticles as a Function of the Organic Shell Design
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Aurélie Walter Audrey Parat Antonio Garofalo Sophie Laurent Luce Vander Elst Robert N. Muller Tao Wu Emilie Heuillard Eric Robinet Florent Meyer Delphine Felder‐Flesch Sylvie Begin‐Colin 《Particle & Particle Systems Characterization》2015,32(5):552-560
Nanoparticles (NPs) with a mean diameter of 10 nm are functionalized with three dendrons: D1 a PEGylated PAMAM dendron of generation 0.5, D2 a hydrophilic oligoethyleneglycol‐derivatized dendron (D2) displaying a phosphonic acid at the focal point, and D2–2P the same dendron than D2 but with two phosphonic acid anchoring agents. Their grafting is confirmed by IR spectroscopy and elemental analysis. All dendronized NPs are stable over a long period of time in suspensions in water and in different physiological media and display a mean hydrodynamic diameter smaller than 50 nm whatever the molecule architecture. NMRD profiles and relaxivity measurements highlight the influence of the molecule architecture on the water diffusion close to the magnetic core thus influencing the relaxation properties at low magnetic field. The high hydrophilic architecture of the dendron D2 by contrast to dendron D1 allows maintaining the colloidal stability in different conditions while ensuring a very good accessibility of water molecule close to the magnetic core. Coupling of a fluorescent dye on dendrons have allowed investigating the biodistribution of dendronized NPs, which are found to be quickly eliminated through urinary and hepatobiliary pathways within 4 h. Furthermore, no enhanced permeation and retention effect in tumors can be observed. 相似文献
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