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21.
Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands
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Elise Salanouve Ghania Bouzemame Dr. Sébastien Blanchard Dr. Etienne Derat Dr. Marine Desage‐El Murr Prof. Louis Fensterbank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4754-4761
Tandem C?H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere C?H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands. 相似文献
22.
Marcileia Zanatta Dr. Anne‐Lise Girard Nathalia M. Simon Prof. Gunter Ebeling Prof. Hubert K. Stassen Prof. Paolo R. Livotto Prof. Francisco P. dos Santos Prof. Jairton Dupont 《Angewandte Chemie (International ed. in English)》2014,53(47):12817-12821
1‐n‐Butyl‐2,3‐dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2‐Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses. 相似文献
23.
Spectroscopy Investigation on Conformational Transition of Tea Glycoconjugate from Green Tea 总被引:5,自引:0,他引:5
The conformational transition of a new glycoconjugate, tea glycoconjugate (TGC), was investigated by spectroscopy techniques including circular dichroism (CD) and ultraviolet (UV) spectroscopy. The solution behaviors of TGC in the mediums of different temperature, pH value, and ions were compared. Results showed that the native conformation of TGC was partially ordered. The CD value and UV absorbance of TGC altered with the change of pH value, temperature, the addition of ions, and also accompanied order-disorder transition. Especially the conditions with temperature higher than the glass transition temperature (Tg=62℃), higher pH value or lower pH value will have the most impact on the conformation of TGC, which will destroy the hydrogen bonds between the TGC molecules. The results indicated that the outside factors play important roles on the stability of the conformation of TGC. 相似文献
24.
A. Akindinov A. Alici P. Antonioli S. Arcelli M. Basile F. Bellini D. Caffarri G. Cara Romeo L. Cifarelli F. Cindolo A. De Caro D. De Gruttola S. De Pasquale K. Doroud M. Fusco Girard B. Guerzoni D. Hatzifotiadou W. W. Jung D. W. Kim J. S. Kim S. Kiselev G. Laurenti K. Lee S. C. Lee D. Malkevich A. Margotti R. Nania A. Nedosekin F. Noferini P. Pagano A. Pesci O. Pinazza R. Preghenella M. Ryabinin E. Scapparone G. Scioli J. Seo A. Silenzi K. Voloshin M. C. S. Williams C. Zampolli A. Zichichi 《The European Physical Journal C - Particles and Fields》2010,68(3-4):601-607
The Time-Of-Flight detector (TOF) of the ALICE experiment at the CERN LHC is based on Multi-gap Resistive Plate Chambers (MRPCs). The TOF detector consists of 152928 readout channels covering a total area of 141 m2. In this paper the results of the calibration with cosmic-ray data collected during 2009 are presented. 相似文献
25.
T.E. Itina L. Patrone W. Marine M. Autric 《Applied Physics A: Materials Science & Processing》1999,69(7):S59-S65
The results of numerical simulation of pulsed laser ablation both in vacuum and into a background gas are presented. The influences of different processes, such as time evolution of the surface temperature, interspecies interactions (elastic collisions, recombination-dissociation reaction), interaction with an ambient gas, and excitations-relaxation processes on time-of-flight (TOF) distributions are examined. Experimentally obtained time-of-flight distributions are further analyzed, based on the results of numerical simulation. It is found that with the aid of numerical results one can explain not only the shape of the TOF distribution, but also the distance dependency of its maximum position (mean delay time). In addition, the mechanisms leading to the appearance of bimodal time-of-flight distribution are revealed. The study presents particular interest for the analysis of experimental results obtained during pulsed laser ablation. 相似文献
26.
Mellot-Draznieks C Girard S Férey G 《Journal of the American Chemical Society》2002,124(51):15326-15335
The design of new and interesting inorganic frameworks is an ongoing challenge in materials sciences. New structures containing double-four-ring (D4R) units have recently received particular attention. The present work focuses on the computational design of new three-dimensional frameworks made of D4R units exclusively. In a first step, our simulations explore the possible ways to assemble predefined D4R units in 3D space using a sophisticated cascade of simulated annealing/minimizations steps (autoassembly of secondary building units method). While the existing zeotype topologies were successfully generated, new topologies were predicted including very open frameworks containing new types of cages. In a second step, lattice energy minimizations were performed to estimate the viability of these hypothetical frameworks as silicate, aluminophosphaste, and gallophosphate candidates. When comparing the hypothetical structures to existing compounds, our results raise the challenging question of the appropriate chemical composition that should be aimed at for a given framework topology of interest. 相似文献
27.
In basic medium, dimethyl 3,3'-dithiopropionate generates methyl acrylate, which serves in situ as a source of propionate moiety. This property was applied to the alkylation of indoles and other nitrogen heterocycles leading to a series of 3-(heteroaryl-substituted) propionates. A mechanistic rationale for the generation of acrylate is presented along with supportive experimental data. 相似文献
28.
In a pair of atoms in collision, the polarizability of the system depends on the relative velocity. The mechanism introduced here implies the time dependence of the effective field acting on the partners. The linear term of the expansion with respect to the velocity suggests the existence of an optical activity for a monatomic fluid submitted to a non-uniform flow. 相似文献
29.
Joshua Rokach Yves Girard Yvan Guindon Joseph G. Atkinson Marie Larue Robert N. Young Paul Masson George Holme 《Tetrahedron letters》1980,21(16):1485-1488
The synthesis and biological characteristics of an SRS-like leukotriene are described. 相似文献