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61.
A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions
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Dr. Christopher J. Wallis Dr. Gilles Alcaraz Dr. Alban S. Petit Dr. Amalia I. Poblador‐Bahamonde Dr. Eric Clot Dr. Christian Bijani Dr. Laure Vendier Dr. Sylviane Sabo‐Etienne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13080-13090
We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a 15N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process. 相似文献
62.
From the N‐Heterocyclic Carbene‐Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates
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Winnie Nzahou Ottou Damien Bourichon Dr. Joan Vignolle Anne‐Laure Wirotius Dr. Fredéric Robert Prof. Yannick Landais Dr. Jean‐Marc Sotiropoulos Dr. Karinne Miqueu Prof. Daniel Taton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9447-9453
Among various N‐heterocyclic carbenes (NHCs) tested, only 1,3‐bis(tert‐butyl)imidazol‐2‐ylidene (NHCtBu) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC‐catalyzed 1,4‐addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well‐defined α‐alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N‐dimethylformamide at 25 °C. A hydroxyl‐terminated poly(ethylene oxide) (PEO‐OH) macro‐initiator was also employed to directly access PEO‐b‐PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHCtBu. 相似文献
63.
Mathieu Brun Jean‐François Chateaux Anne‐Laure Deman Patrick Pittet Rosaria Ferrigno 《Electroanalysis》2011,23(2):321-324
This paper presents an alternative approach to create low‐cost and patternable carbon electrodes suitable for microfluidic devices. The fabrication and the electrochemical performances of electrodes made of Polydimethylsiloxane doped with commercially available carbon black (C‐PDMS) are described. Conductivity and electrochemical measurements performed on various carbon to PDMS ratios showed that electrodes with suitable electrochemical properties were obtained with a ratio of 25 %. 相似文献
64.
Memboeuf A Jullien L Lartia R Brasme B Gimbert Y 《Journal of the American Society for Mass Spectrometry》2011,22(10):1744-1752
Collision induced dissociation tandem mass spectrometry experiments were performed to unequivocally separate compounds from
an isobaric mixture of two products. The Survival Yield curve was obtained and is shown to consist in a linear combination
of the curves corresponding to the two components separately. For such a mixture, a plateau appears on the diagram in lieu
of the continuous decrease expected allowing for the structural study of the two components separately. The width of the plateau
critically relates to the fragmentation parameters of the two molecular ions, which need to be sufficiently different structurally
for the plateau to be observed. However, at constant fragmentation parameters, we have observed the width significantly increases
at large m/z. This makes the separation more and more efficient as isobars have larger m/z and the technique complementary to those applicable at low m/z only. We have observed that the vertical position of the plateau relates linearly to the relative concentration of the two
compounds that may be useful for quantification. Repeatability was estimated at 2% on a quadrupole ion trap. An advantage
of using survival yield curves only, is that a priori knowledge of the respective fragmentation patterns of the two isobars
becomes unnecessary. Consequently, similar performances are obtained if fragments are isobaric, which is also demonstrated
in our study. The critical case of reverse peptides, at low m/z and similar fragmentation parameters, is also presented as a limitation of the method. 相似文献
65.
The structure and thermodynamic properties of lanthanide complexes with a new tripodal ligand L2 have been elucidated using different physicochemical methods. At stoichiometric ratios, the tetrahedral three-dimensional complexes with lanthanide cations are formed in acetonitrile with good stabilities. Despite minor structural changes comparing to previously investigated tripodal ligands, the resulting assembly exhibits different features revealed with the crystal structure of [Eu(4)L2(4)](OH)(ClO(4))(11) (orthorhombic, Pbcn). Interestingly, the highly charged edifice contains an inner cage encapsulating a perchlorate anion. Such lanthanide mediated cage-like assemblies are rare, and may be of interest for different sensing applications. Indeed, the anionic guest can be exchanged with different anions. The related host-guest equilibria were investigated with NMR techniques. Various aspects of these reactions are qualitatively discussed. 相似文献
66.
Palmer SJ Grand LM Frost RL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(1):156-160
Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum. 相似文献
67.
68.
Mérièm Anouti Amina Mirghani Johan Jacquemin Laure Timperman Hervé Galiano 《Ionics》2013,19(12):1783-1790
Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV–visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs. 相似文献
69.
Patrick Rozier Laure Vendier Jean Galy 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):i111-i113
A single crystal of KVTeO5, potassium vanadium tellurite, has been grown. The present structure determination has been conducted together with the refinement of the NaVTeO5 homologue, sodium vanadium tellurite, for the sake of precise comparison. The network consists of [VTeO5]n ribbons built up by VO4 tetrahedra linking centrosymmetric Te2O6 groups and stacked along the [010] direction; the alkali cations are intercalated in between. The TeIV atom exhibits a typical one‐sided coordination number (CN) of 4, completed by a lone pair, which forms a distorted triangular bipyramid with the four O atoms. 相似文献
70.
In this work we consider a two steps finite volume scheme, recently developed to solve nonhomogeneous systems. The first step of the scheme depends on a diffusion control parameter which we modulate, using the limiters theory. Results on Shallow water equations and two phase flows are presented. 相似文献