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排序方式: 共有3137条查询结果,搜索用时 29 毫秒
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Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
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Mariem Ghali Chaima Brahmi Mahmoud Benltifa Cyril Vaulot Aissam Airoudj Philippe Fioux Frédéric Dumur Corine Simonnet-Jégat Fabrice Morlet-Savary Salah Jellali Latifa Bousselmi Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2021,59(2):153-169
Different inorganic/organic photocomposites based on polyoxometalate (POM) nanoparticles have been developed for photocatalytic applications. Currently, polyoxometalate nanoparticles have been successfully in-situ embedded into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The proposed POM/polymer photocomposites have been characterized using complementary techniques for a better understanding of their photocatalytic activity. Interestingly, the obtained photocomposites exhibit high rigidity, excellent thermal stability, a non-negligible porosity and new functionalities such as light reactivity and redox properties. Moreover, developed composites showed efficient catalytic activity for the color removal of aqueous solutions of erythrosine and rose Bengal under Light Emitting Diodes LED@375 nm irradiation reaching 80 and 90% as a final color removal, respectively. 相似文献
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Romain Bénéteau Anne Boussonnière Jean‐Christophe Rouaud Prof. Dr. Jacques Lebreton Dr. Jérôme Graton Prof. Dr. Denis Jacquemin Dr. Muriel Sebban Prof. Dr. Hassan Oulyadi Ghanem Hamdoun Dr. Amber N. Hancock Prof. Dr. Carl H. Schiesser Dr. Fabrice Dénès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4809-4824
α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences. 相似文献
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Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
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Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Fabrice Morlet‐Savary Jean Pierre Fouassier Didier Gigmes Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(24):2860-2866
Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1‐ANH8) have been prepared and combined with an iodonium salt (and optionally N‐vinylcarbazole) or an amine (and optionally 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (~ 12 mW cm?2), laser diode at 405 nm (~1.5 mW cm?2) or blue LED centered at 455 nm (80 mW cm?2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well‐known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin‐trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2860–2866 相似文献
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Structure/reactivity/photoinitiation ability relationships in novel benzo pyrazolo (or imidazo) isoquinolinone derivatives upon visible light LEDs 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Mariem Bouzrati‐Zerelli Bernadette Graff Didier Gigmes Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(15):1806-1815
Isoquinolinone derivatives bearing amino‐ or nitro‐ substituent (IQNs) have been synthesized as photoinitiators and combined with various additives (i.e., iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)?1,3,5‐triazine) to initiate ring‐opening cationic polymerizations (CP) or free radical polymerizations under exposure to visible LEDs (e.g., LEDs at 405 nm or 455 nm, or cold white LED) or a halogen lamp. Compared to the well‐known camphorquinone‐based systems, the novel IQNs‐based combinations employed here demonstrate higher efficiencies for the CP of epoxides. The photochemically generated reactive species (i.e., cations and radicals) from the IQNs‐based systems have been investigated by steady state photolysis, cyclic voltammetry, fluorescence, laser flash photolysis, and electron spin resonance spin trapping techniques. The structure/reactivity/photoinitiating ability relationships of IQNs‐based combinations are also discussed; the crucial role of the excited state lifetimes of the photoinitiators to ensure efficient quenching by additives is clearly underlined. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1806–1815 相似文献
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