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941.
Wanglee YJ Hu J White RE Lee MY Stewart SM Perrotin P Scott SL 《Journal of the American Chemical Society》2012,134(1):355-366
A supported, single-site Lewis acid, ≡SiOB(C(6)F(5))(2), was prepared by water-catalyzed grafting of B(C(6)F(5))(3) onto the surface of amorphous silica, and its subsequent use as a cocatalyst for heterogeneous olefin polymerization was explored. Although B(C(6)F(5))(3) has been reported to be unreactive toward silica in the absence of a Br?nsted base, we find that it can be grafted even at room temperature, albeit slowly. The mechanism was investigated by (1)H and (19)F NMR, in both the solution and solid states. In the presence of a trace amount of H(2)O, either added intentionally or formed in situ by borane-induced dehydration of silanol pairs, the adduct (C(6)F(5))(3)B·OH(2) hydrolyzes to afford C(6)F(5)H and (C(6)F(5))(2)BOH. The latter reacts with the surface hydroxyl groups of silica to yield ≡SiOB(C(6)F(5))(2) sites and regenerate H(2)O. When B(C(6)F(5))(3) is present in excess, the resulting grafted boranes appear to be completely dry, due to the eventual formation of [(C(6)F(5))(2)B](2)O. The immobilized, tri-coordinate Lewis acid sites were characterized by solid-state (11)B and (19)F NMR, IR, elemental analysis, and C(5)H(5)N-TPD. Their ability to activate two molecular C(2)H(4) polymerization catalysts, Cp(2)ZrMe(2) and an (α-iminocarboxamidato)nickel(II) complex, was explored. 相似文献
942.
Kerber RN Kermagoret A Callens E Florian P Massiot D Lesage A Copéret C Delbecq F Rozanska X Sautet P 《Journal of the American Chemical Society》2012,134(15):6767-6775
The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studied as a model for a supported methylaluminoxane and aluminum cocatalyst. While (27)Al solid-state NMR spectroscopy would be a method of choice, it has been difficult to apply this technique because of large quadrupolar broadenings. Here, from a combined use of the highest stable field NMR instruments (17.6, 20.0, and 23.5 T) and ultrafast magic angle spinning (>60 kHz), high-quality spectra were obtained, allowing isotropic chemical shifts, quadrupolar couplings, and asymmetric parameters to be extracted. Combined with first-principles calculations, these NMR signatures were then assigned to actual structures of surface aluminum sites. For silica (here SBA-15) reacted with triethylaluminum, the surface sites are in fact mainly dinuclear Al species, grafted on the silica surface via either two terminal or two bridging siloxy ligands. Tetrahedral sites, resulting from the incorporation of Al inside the silica matrix, are also seen as minor species. No evidence for putative tri-coordinated Al atoms has been found. 相似文献
943.
Dr. Delphine Crozet Dr. Aitor Gual Dr. David McKay Dr. Chiara Dinoi Dr. Cyril Godard Prof. Martine Urrutigoïty Dr. Jean‐Claude Daran Prof. Laurent Maron Prof. Carmen Claver Prof. Philippe Kalck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7128-7140
The reactivity of [Rh(CO)2{(R,R)‐Ph? BPE}]BF4 ( 2 ) toward amine, CO and/or H2 was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)3{(R,R)‐Ph? BPE}]BF4 ( 4 ) and [Rh(CO)2(NHC5H10){(R,R)‐Ph‐BPE}]BF4 ( 8 ) were identified. The transformation of 2 into the neutral complex [RhH(CO)2{(R,R)‐Ph? BPE}] ( 3 ) under hydroaminomethylation conditions (CO/H2, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)2(CO)2{(R,R)‐Ph? BPE}]BF4 ( 6 ), resulting from the oxidative addition of H2 on 2 . 相似文献
944.
Dr. Stefan Wuttke Dr. Philippe Bazin Dr. Alexandre Vimont Dr. Christian Serre Dr. You‐Kyong Seo Dr. Young Kyu Hwang Dr. Jong‐San Chang Prof. Gérard Férey Prof. Marco Daturi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(38):11959-11967
A reducible MIL‐100(Fe) metal–organic framework (MOF) was investigated for the separation of a propane/propene mixture. An operando methodology was applied (for the first time in the case of a MOF) in order to shed light on the separation mechanism. Breakthrough curves were obtained as in traditional separation column experiments, but monitoring the material surface online, thus providing evidences on the adsorption sites. The qualitative and quantitative analyses of FeII and, to some extent, FeIII sites were possible, upon different activation protocols. Moreover, it was possible to identify the nature and the role of the active sites in the separation process by selective poisoning of one family of sites: it was clearly evidenced that the unsaturated FeII sites are mainly responsible for the separation effect of the propane/propene mixture, thanks to their affinity for the unsaturated bonds, such as the C?C entities in propene. The activity of the highly concentrated FeIII sites was also highlighted. 相似文献
945.
Louis‐Philippe B. Beaulieu Dr. Lucie E. Zimmer Prof. Alexandre Gagnon Prof. André B. Charette 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14784-14791
Herein, we report the enantio‐ and diastereoselective formation of trans‐iodo‐ and trans‐chlorocyclopropanes from α‐iodo‐ and α‐chlorozinc carbenoids by using a dioxaborolane‐derived chiral ligand. The synthetically useful iodocyclopropane building blocks were derivatized by an electrophilic trapping of the corresponding cyclopropyl lithium species or a Negishi coupling to give access to a variety of enantioenriched 1,2,3‐substituted cyclopropanes. The synthetic utility of this method was demonstrated by the formal synthesis of an HIV‐1 protease inhibitor. In addition, the related stereoselective bromocyclopropanation was also investigated. New insights about the relative electrophilicity of haloiodomethylzinc carbenoids are also presented. 相似文献
946.
Pahari B Mhadhbi N Corbel G Lacorre P Dittmer J 《Dalton transactions (Cambridge, England : 2003)》2012,41(18):5696-5703
The effect of partial substitution of molybdenum by phosphorus on the global and local structural arrangement of the fast oxide-ion conductor La(2)Mo(2)O(9) (LAMOX) has been studied by X-ray powder diffraction as well as (139)La and (31)P solid state NMR. The diffraction patterns show that La(2)Mo(2-y)P(y)O(9-y/2) forms a solid solution at low phosphorus concentrations, and that there is a structural phase transition upon increasing phosphorus concentration. This phase transition is also reflected in (139)La and (31)P NMR spectra. The possibility to excite (31)P multiple-quantum coherences of one of the (31)P NMR signals gives evidence of an accumulation of phosphorus atoms on neighbouring Mo-type sites already before formation of three-dimensional precipitates. On the basis of our X-ray and NMR results we propose a possible structural arrangement of the compound La(2)Mo(2-y)P(y)O(9-y/2) that explains the experimental observations by crystal twinning. 相似文献
947.
948.
Philippe Colomban Aurlie Tourni Maria Cristina Caggiani Cline Paris 《Journal of Raman spectroscopy : JRS》2012,43(12):1975-1984
On‐site Raman spectroscopy is used to investigate four mosque lamps and a bottle dating back to the 13–14th centuries (Syria and/or Egypt, Mamluk period) from the Department of Islamic Art, Musée du Louvre, Paris. The pigments and the enamelled glass matrix have been identified in order to discuss their technology. A comparison is made with one masterpiece from the 19th century made by Brocard. The results obtained for blue (lapis lazuli or Co‐coloured glass), yellow (Naples yellows or zinc/chrome yellow), green (mixture of the aforementioned blue and yellow pigments or lead chromate for restorated foot) red (hematite), white (cassiterite or arsenate) and pink (hematite and cassiterite) pigments are presented. The consistency of the pigments period of use/technology with the datation proposed for each artefact is evaluated. For one lamp, the detection of quartz in some places of the hematite‐rich glassy layer supporting the gold is related to the search of a physical bonding with the artefact body. Carbon residues in such enamel are consistent with the use of an organic medium to place the enamel powder before the firing. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
949.
Yannick Crémillieux Florent Goutailler Bruno Montcel Dominique Grand Gérard Vermeulen Pierre-Etienne Wolf 《Applied magnetic resonance》2012,43(1-2):167-180
The volume of polarized sample and the delay required between successive polarizations of samples represent serious constraints for dynamic nuclear polarization (DNP) applications. With these limitations in mind, a DNP polarizer, based on a super-wide bore (150-mm diameter) vertical magnet operating at 3.35?T, was designed. The working diameter for loading/unloading samples is equal to 46?mm and the microwave cavity can accommodate up to three samples. The cryostat can be cooled to 4.2?K in typically 2?h and filled with liquid helium in 1?h. Once filled with liquid helium, the cryostat hold time is on the order of 4?h and a minimum temperature of 1.19?K can be reached. In situ polarization levels at low temperature were measured between 5 and 10?% in single and multiple samples of 13C-labeled urea and glycine. 相似文献
950.
Kissi Benaissa Parron Vera Miguel Angel Rubio Cintas Maria Dlolores Dubujet Philippe Khamlichi Abdellatif Bezzazi Mohammed El Bakkali Larbi 《Applied Mathematical Modelling》2012
CFD simulation with enhanced modeling of turbulence and near-wall treatment is used to model water–clay mixtures flowing through a cylindrical pipe domain. Effects on the wall-shear stress resulting from varying water clay content and applied hydraulic gradient are analyzed. Various parametric studies were performed and had shown that the two-dimensional modelling introduced in the present study does not yield a uniform wall-shear stress along the pipe wall and that clay concentration affects significantly the wall-shear stress value. This is in contrast with the common hypothesis used in one-dimensional modeling approaches where this stress is assumed constant and which gives rise to uniform erosion along the pipe wall. The obtained results had enabled predicting more realistically erosion amount and had allowed for understanding the irregular eroded hole wall shape as observed experimentally after performing the standard hole erosion test. 相似文献