Search results for "Catalysis"

Deprotonation of Thiophenes Using Lithium Magnesates.

2005

Abstract Thiophene was regioselectively deprotonated at C2 on treatment with 1/3 equiv of Bu3MgLi in THF at room temperature. The lithium arylmagnesate formed was either trapped with electrophiles or cross-coupled in a ‘one-pot’ procedure with aryl halides under palladium catalysis. 2-Chlorothiophene and 2-methoxythiophene were similarly deprotonated at C5 under the same reaction conditions. The enhancement of the reactivity of the base using TMEDA was evidenced using 1H NMR spectroscopy.

ChemInform Abstract: Efficient Synthesis of Racemic and Chiral Alkenyl Sulfoxides by Palladium-Catalyzed Suzuki Coupling.

2010

Alkenyl sulfoxide derivatives are obtained in high yields through a palladium-catalyzed Suzuki/Miyaura cross-coupling reaction of racemic and chiral 1-halo sulfoxides with aryl and alkenyl boronic acids. Chiral substrates react with no loss of optical purity and high optical yields. The reaction takes place with different palladium catalysts, such as Pd(PPh 3 ) 4 or Pd(OAc) 2 /DABCO. Although nitrogen ligands like DABCO lead to an active palladium catalyst, they are less effective than the phosphine ones.

Propriétés et performances de phosphines ferrocéniques dans le couplage C-O, C-S et C-N : nouvelles méthodologies de synthèse au palladium

2012

Multidentate ligands usually show great activities in low loading organometallic catalysis in palladium. Among these ligands, the use of ferrocenyl polyphosphane ligands give interesting results. Robust palladium-ferrocenyl triphosphane catalytic systems have permitted to obtain biarylamines and aryl-heteroaryl ethers in the presence of low catalytic loadings. DFT studies on catalytic cycle during formation of aryl-heteroaryl ethers were carried out. The presence of third phosphino group stabilizes a transition state which enhances the rate of the reductive elimination. Triarylamines were obtained with ferrocenyl diphosphane in the presence of 2 mol% of palladium loading. Moderate to excell…

Phosphine-diène and Salicylamidines ligands : coordination chemistry, catalysis and therapy

2017

The subject of this thesis concerns the development of new ligands, their coordination chemistry, and the synthesis of the corresponding metal complexes for catalysis and therapy.The first part of this work relates to the synthesis of diene-phosphine ligands, their saturated analogs, and the corresponding arene-ruthenium complexes. Arene decoordination allows the formation of a cationic bimetallic complex where the ligand is diène-η4/κ-P coordinated to the ruthenium. These complexes have been applied to atom transfer radical addition (ATRA) of CCl4 to styrene. When harsh reaction conditions are used, the superiority of the “diene” complexes is highlighted comparing to saturated analogs.The …

Real-time detection of highly oxidized organosulfates and BSOA marker compounds during the F–BEACh 2014 field study

2017

Abstract. The chemical composition of organic aerosols was analyzed using complementary mass spectrometric techniques during a field study in Central Europe in July 2014 (Fichtelgebirge – Biogenic Emission and Aerosol Chemistry, F–BEACh 2014). Aerosols were analyzed in real-time by Aerosol Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (AeroFAPA–MS), Aerosol Mass Spectrometry (AMS), and Chemical Ionization Atmospheric-Pressure interface Time-of-Flight Mass Spectrometry (CI–APiToF–MS). In addition, offline detection of acidic organic compounds was conducted by non-target screening of filter samples using High Resolution Mass Spectrometry (HRMS) in combination with Ultra-High Pressu…

General overview: European Integrated project on Aerosol Cloud Climate and Air Quality interactions (EUCAARI)-integrating aerosol research from nano …

2011

In this paper we describe and summarize the main achievements of the European Aerosol Cloud Climate and Air Quality Interactions project (EUCAARI). EUCAARI started on 1 January 2007 and ended on 31 December 2010 leaving a rich legacy including: (a) a comprehensive database with a year of observations of the physical, chemical and optical properties of aerosol particles over Europe, (b) comprehensive aerosol measurements in four developing countries, (c) a database of airborne measurements of aerosols and clouds over Europe during May 2008, (d) comprehensive modeling tools to study aerosol processes fron nano to global scale and their effects on climate and air quality. In addition a new Pan…

2012

Abstract. The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a …

Comparison between catalytic and catalytic photo-assisted propene hydration by using supported heteropolyacid

2012

Abstract Hybrid materials have been prepared by impregnation of the heteropolyacid H 3 PW 12 O 40 on commercial TiO 2 . The polyoxometalates (POM) amount deposited was 15, 30, 50 and 70% with respect to the weight of the TiO 2 support. Moreover two samples containing a POM amount of 15, and 50% with respect to the weight of SiO 2 were also prepared for the sake of comparison. All prepared samples were efficient catalysts for the hydration of propene to 2-propanol in gas–solid regime at atmospheric pressure and at temperatures ranging between 50 and 85 °C. The study carried out on the hybrid TiO 2 based materials evidenced that, as far as the catalytic activity is concerned, exists an optimu…

l -Prolinoyl chiral picket iron porphyrins evaluated for the enantioselective epoxidation of alkenes

2003

International audience; Four atropisomers of an L-prolinoyl picket porphyrin were synthesised from tetra-o-aminophenyl porphyrin (TAPP) and were evaluated as alkene epoxidation catalysts after incorporation of iron in the porphyrin core. In the case of the aaaa atropisomer bearing the four amino groups on the same side, a bulky base was employed in order to suppress the eventual reaction on the non-functionalised side of the porphyrin.The resulting enantioselectivities were compared with either other chiral motifs or with the corresponding strapped porphyrins. The enantioselectivities obtained with picket porphyrins are as high as those for strapped porphryins, and in some cases, even highe…

Metal-support and preparation influence on the structural and electronic properties of gold catalysts

2006

Abstract Nanostructured gold catalysts supported on CeO2 and SiO2 were prepared by the deposition–precipitation (DP) and the solvated metal atom dispersion (SMAD) techniques. The structural and electronic properties of the catalysts were investigated by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Gold was found as small metal nanoparticles (cluster size ∼2 nm) in the SMAD-prepared samples and in ionic state in the DP catalysts. The catalytic activity of the samples was tested in the reaction of low temperature CO oxidation. Gold nanosized particles in a pure metallic state exhibited a worse catalytic performance, both on ceria and…