Search results for "hydrogenation"
showing 10 items of 155 documents
ChemInform Abstract: Cross-Dehydrogenative Couplings Between Indoles and β-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation vi…
2014
Cross-dehydrogenative coupling reactions between β-ketoesters and electron-rich arenes, such as indoles, proceed with high regiochemical fidelity with a range of β-ketoesters and indoles. The mechanism of the reaction between a prototypical β-ketoester, ethyl 2-oxocyclopentanonecarboxylate, and N-methylindole has been studied experimentally by monitoring the temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments. DFT calculations have been carried out using a dispersion-corrected range-separated hybrid functional (ωB97X-D) to explore the basic elementary steps of the catalytic cycle. The experimental results indicate that the reaction proceeds v…
Cross-Dehydrogenative Couplings between Indoles and beta-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a Proton-Assiste…
2014
Cross-dehydrogenative coupling reactions between β-ketoesters and electron-rich arenes, such as indoles, proceed with high regiochemical fidelity with a range of β-ketoesters and indoles. The mechanism of the reaction between a prototypical β-ketoester, ethyl 2-oxocyclopentanonecarboxylate, and N-methylindole has been studied experimentally by monitoring the temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments. DFT calculations have been carried out using a dispersion-corrected range-separated hybrid functional (ωB97X-D) to explore the basic elementary steps of the catalytic cycle. The experimental results indicate that the reaction proceeds v…
Selectivity in Propene Dehydrogenation on Pt and Pt3Sn Surfaces from First Principles
2013
Propene can be produced via dehydrogenation of propane on Pt-based catalysts; however, the catalysts are plagued by low selectivity toward propene and high coke formation. The selectivity can be improved and the coke formation reduced by alloying Pt with Sn. The alloying is known to weaken the binding of propene, which in part explains the improved performance. We conducted density functional theory calculations to study the dehydrogenation of propene on flat and stepped Pt and Pt3Sn surfaces. The steps on Pt dehydrogenate propene readily, whereas, on Pt3Sn, the steps are inert because they are decorated with Sn. Our results indicate that the high selectivity and low coking on the Pt–Sn cat…
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
2011
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral liga…
Oxidative dehydrogenation of n-butane on MgO-supported vanadium oxide catalysts
1998
Abstract Vanadium–magnesium oxide (VMgO) catalysts have been prepared, characterized and tested in the ODH of n-butane. The catalysts were prepared by two variations of the wet-impregnation method using aqueous ammonium metavanadate or organically-based methanolic vanadyl acetylacetonate solutions. The catalyst surface area depends on the vanadium content and the preparation method. Catalyst characterization (i.e. XRD, 51V NMR, FTIR, LRS) results indicate the presence of poor crystalline Mg-orthovanadate (Mg3V2O8), while the presence of other Mg-vanadates is not clear. Oxygen isotopic-exchange experiments on VMgO catalysts indicate an R2 process: [ 18 O 2 +2 16 O 2− (s) → ( 18 O 18 O 16 O 1…
Polypyrrole–palladium nanoparticles composite as efficient catalyst for Suzuki–Miyaura coupling
2012
International audience; Synthesis of a new hybrid material (Pd/PPy) composed of polypyrrole globules with uniformly incorporated Pd nanoparticles via direct redox reaction between pyrrole and Pd(NH3)(4)Cl-2 in water has been recently reported (V.A. Zinovyeva, M.A.Vorotyntsev, I. Bezverkhyy, D. Chaumont, J.-C. Hierso, Adv. Funct. Mater. 21 (2011) 1064-1075). In the actual study, this procedure has been extended to synthesize a series of Pd/PPy powders with variable palladium content and morphological parameters. Depending on the monomer-to-oxidant ratio in reaction mixture, average diameters of Pd and PPy particles may change in the ranges of 1.25-1.45 and 27-62 nm, respectively, the Pd conc…
Selective Oxidation of n-Butane and Butenes over Vanadium-Containing Catalysts
2000
Abstract The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg–Al mixed oxides with Mg/(Al+Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C4-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reac…
Gas-phase hydrogenation of propionitrile on copper-lanthanide oxides
2009
Abstract The hydrogenation of propionitrile on copper-lanthanide oxide catalysts (2Cu·CeO 2 and 4Cu·Ln 2 O 3 (Ln = La, Pr, Nd)) was studied in the gas phase. The activity of the catalysts varies with the lanthanide in the order 2Cu·CeO 2 > 4Cu·Pr 2 O 3 > 4Cu·La 2 O 3 ≥ 4Cu·Nd 2 O 3 , while the activation energies varies in the opposite order, except for 2Cu·CeO 2 . The main product was the primary amine, n -propylamine. The formation of the unstable imine CH 3 CH 2 N CHCH 3 as a major product over 2Cu·CeO 2 seems to be consistent with the acidity of the catalyst. The catalysts were more selective than conventional copper impregnation catalysts, Cu (10 wt.%) on SiO 2 , La 2 O 3 or CeO 2 ,…
Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts
1996
Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.
Cis-15 intermediates of biohydrogenation in the duodenal flow of cows receiving linseed
2006
Duodenal samples from a previous experiment (Akraim et al., 2006) were reanalysed for determination of cis-15 intermediates of ruminal biohydrogenation (BH). Three dry Holstein cows fitted with a duodenal cannula received a diet with 14% (dry matter basis) raw linseed. C18 fatty acids (C18FA) represented 6.3% of dietary dry matter, and contained 57.8% of C18:3. After 18 days adaptation, on each cow, twelve samples of duodenal flow were taken over 3 days, composited, and analysed for FA composition. Cis-9,trans-11,cis-15C18:3 and trans-11,cis-15C18:2 (CLnA) were identified by GC-MS. The proportion of CLnA was low, in spite of the high C18:3 intake. The first step of C18:3 BH, isomerisation t…