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Rh Catalyst (rh + catalyst)
Selected AbstractsAsymmetric Hydrogenation with Highly Active IndolPhos,Rh Catalysts: Kinetics and Reaction MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2010Jeroen Wassenaar Abstract The mechanism of the IndolPhos,Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis,Menten kinetics. A large value of KM (KM=5.01±0.16,M) is obtained, which indicates that the Rh,solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate,catalyst complexes, which are undetectable by experimental means, suggest that the major substrate,catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism of asymmetric hydrogenation reactions with C1 -symmetric heteroditopic and monodentate ligands. [source] The Immobilization of Rhodium-4-(diphenylphosphino)-2- (diphenylphosphinomethyl)-pyrrolidine (Rh-PPM) Complexes: A Systematic StudyADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006Benoît Pugin Abstract A modular toolbox for the immobilization of homogeneous catalysts to various supports is described. It consists of functionalized chiral diphosphines and three different linkers based on isocyanate chemistry and it is used to attach the 4-(diphenylphosphino)-2-(diphenylphosphinomethyl)-pyrrolidine (PPM) ligand to a large variety of soluble, swellable and non-swellable solid organic polymers and to silica gels. As model reaction the hydrogenation of acetamidocinnamic acid derivatives, catalyzed with high enantioselectivity was chosen. Besides information on the usefulness of a particular type of support for synthetic applications, the experiments were also designed to address the question how parameters such as solubility, swellability, cage or pore size and solvent affect the rate and enantioselectivity of an immobilized catalyst. Rhodium complexes of ligands attached to soluble polymers and inorganic supports achieved ees up to 95,% and turnover frequencies between 700 and 1400,h,1, very close to the values of the homogeneous Rh catalyst (ee 95,%, TOF 1320,h,1). Insoluble or strongly cross-linked organic polymers led to catalysts with lower enantioselectivity and activity. PPM ligands attached to water soluble dendrimer fragments allowed hydrogenation in water solution with ees up to 94,%, albeit with much lower activity compared to reactions in methanol with the homogeneous catalyst. [source] Hydrogen generation in a reverse-flow microreactor: 1.AICHE JOURNAL, Issue 8 2005Model formulation, scaling Abstract A 1-D model for methane partial oxidation in a tubular microreactor is considered. This work is motivated by a recent report by Kikas et al. that experimentally demonstrated the possibility of autothermal generation of hydrogen by partial oxidation of methane in a tubular microreactor. The reactor consists of four cylindrical channels, each 500 microns in diameter, containing Pt/13%,Rh catalyst. Autothermal generation of hydrogen was possible in both unidirectional (UD) and reverse-flow (RF) operations of the reactor, with the RF operation providing better hydrogen yield and lower temperatures than those of the UD operation. Critical comparison of methane oxidation and reforming kinetics from the literature is performed. An analysis of the timescales of individual processes within the reactor is presented to gain fundamental insight into the reactor operation. Finally, the effect of radiation heat transfer is also considered, and it is found to play an important role for a shorter-size reactor. © 2005 American Institute of Chemical Engineers AIChE J, 2005 [source] The asymmetric synthesis of (R,R)-formoterol via transfer hydrogenation with polyethylene glycol bound Rh catalyst in PEG2000 and waterCHIRALITY, Issue 2 2010Ling Huang Abstract (R,R)-formoterol was synthesized in seven steps with 4-hydroxyl-3-nitro-acetophenone as the starting material. The key intermediate, the chiral secondary alcohol 4, was prepared via Rh-catalyzed asymmetric transfer hydrogenation with (S,S)-PEGBsDPEN as the ligand and sodium formate as the hydrogen donor under mild conditions. With a mixture of PEG 2000 and water as the reaction media, the catalyst system could be recycled four times. Chirality, 2010. © 2009 Wiley-Liss, Inc. [source] Polymerization of substituted acetylenes by various rhodium catalysts: Comparison of catalyst activity and effect of additivesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2005Atsushi Nakazato Abstract This research deals with comparison of the activity of various Rh catalysts in the polymerization of monosubstituted acetylenes and the effect of various amines used in conjunction with [Rh(nbd)Cl]2 in the polymerization of phenylacetylene. A zwitterionic Rh complex, Rh+(nbd)[(,6 -C6H5)B,(C6H5)3] (3), was able to polymerize phenylacetylene (5a), t -butylacetylene (5b), N -propargylhexanamide (5c) and n -hexyl propiolate (5d), and displayed higher activity than the other catalysts examined, that is [Rh(nbd)Cl]2 (1), [Rh(cod)(O - o -cresol)]2 (2), and Rh-vinyl complex (4). Monomers 5a and 5c polymerized virtually quantitatively or in fair yields with all these catalysts, while monomer 5b was polymerizable only with catalyts 3 and 4. Monomer 5d did not polymerize in high yields with these Rh complexes. The catalytic activity tended to decrease in the order of 3 > 4 > 2 > 1. Although polymerization of 5a did not proceed at all in toluene with [Rh(nbd)Cl]2 alone, it smoothly polymerized in the presence of various amines as cocatalysts. The polymerization rate as well as the molecular weight of polymer depended on the basicity and steric bulkiness of amines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4530,4536, 2005 [source] Synthesis of Substituted Polyacetylenes Grafted with Polystyrene Chains by the Macromonomer Method and Their CharacterizationMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2006Wei Zhang Abstract Summary: A macromonomer (1) consisting of a polystyrene chain and an acetylenic chain end (,=,2,500, ,=,1.20) was prepared by atom transfer radical polymerization. Macromonomer 1 was copolymerized with phenylacetylene (2) and propargyl 2-bromopropionate (3) by using Rh catalysts at varying feed ratios from 10 to 50 wt.-% to produce graft copolymers 4 and 5, respectively. The synthesized copolymers 4 and 5 possessed a conjugated polyene main-chain and polystyrene grafts, and contained 11,34 and 16,77 wt.-% of polystyrene with of 61,400,144,000 and 19,300,22,500, respectively. Graft copolymer 4 was a yellow solid and thermally stable up to 225,°C, whereas 5 was a brown solid with weight loss beginning at 175,°C. Graft copolymers 4 and 5 exhibited UV-vis absorption edges at 525 and 425 nm, respectively, which are attributable to the conjugated main-chain structure. Copolymerization of the acetylene-terminated polystyrene-based macromonomer with monosubstituted acetylenes. [source] Palladium-Catalyzed Desulfitative Mizoroki,Heck Couplings of Sulfonyl Chlorides with Mono- and Disubstituted Olefins: Rhodium-Catalyzed Desulfitative Heck-Type Reactions under Phosphine- and Base-Free ConditionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2005Srinivas Reddy Dubbaka Abstract New conditions have been found for the desulfitative Mizoroki,Heck arylation and trifluoromethylation of mono- and disubustituted olefins with arenesulfonyl and trifluoromethanesulfonyl chlorides. Thus (E)-1,2-disubstituted alkenes with high stereoselectivity and 1,1,2-disubstituted alkenes with 12:1 to 21:1 E/Z steroselectivity can be obtained. Herrmann's palladacycle at 0.1 mol,% is sufficient to catalyze these reactions, for which electron-rich or electron-poor sulfonyl chlorides and alkenes are suitable. If phosphine- and base-free conditions are required, 1 mol,% [RhCl(C2H4)2] catalyzes the desulfitative cross-coupling reactions. Contrary to results reported for [RuCl2(PPh3)2]-catalyzed coupling reactions with sulfonyl chlorides, the palladium and rhodium desulfitative Mizoroki,Heck coupling reactions are not inhibited by radical scavenging agents. Possible sulfones arising from the sulfonylation of alkenes at 60,°C are not desulfitated at higher temperatures in the presence of the Pd or Rh catalysts. De nouvelles conditions sont rapporteés pour les couplages désulfitants du type Mizoroki,Heck des chlorures d'arènesulfonyles et trifluorométhanesulfonyle avec des oléfines mono- et disubstitueés. La méthode permet la synthèse de (E)-alcènes 1,2-disubstitués avec haute stéréosélectivité et d'alkènes 1,1,2-trisubstitués avec des stéréosélectivités E/Z variant de 12:1 à 21:1. La palladacycle de Herrmann à 0.1 mol% est suffisant pour catalyser ces reactions qui peuvent engager des chlorures de sulfonyles et des alcènes soit riches ou pauvres en électron. Si des conditions sans phosphine et sans base sont requises, 1 mol,% de [RhCl(C2H4)2] est un excellent catalyseur pour ces couplages désulfitants. Contrairement à ce qui est rapporté pour des réactions analogues catalysées par [RuCl2(PPh3)2] et qui impliquent des intermédiaires radicalaires, les couplages du type Mizoroki,Heck désulfitants catalysés par des complexes de palladium ou de rhodium ne sont pas inhibés par des pièges à radicaux. De plus, les sulfones qui peuvent se former par sulfonylation des alcènes (60,oC) ne sont pas désulfitées à plus haute température en présence des catalyseurs au Pd ou au Rh. [source] Hydrogenolysis of 1,2-Propanediol for the Production of Biopropanols from GlycerolCHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 6 2010Yasushi Amada Abstract Production of propanols from glycerol, which are known as biopropanols, requires catalysts for the hydrogenolysis of 1,2-propanediol, which has been easily derived from glycerol. It is found that the Rh/SiO2 catalysts modified with ReOxspecies exhibited high activity and selectivity in the hydrogenolysis of 1,2-propanediol to propanols with low selectivity to degradation products and high stability. The optimized RhReOx/SiO2 (Re/Rh=0.5) catalyst gave high yields of 1-propanol (66,%) and propanols (1-propanol +2-propanol) (85,%) in the hydrogenolysis of 1,2-propanediol. In addition, the catalyst was applicable to the one-pot conversion of glycerol to propanols. The structure of Rh metal particles with attached ReOxclusters is suggested from the catalyst characterization. It is proposed that 1,2-propanediol hydrogenolysis proceeds by the hydrogenolysis of the alkoxide species on Re with hydrogen species on the Rh metal surface. [source] | |||||||||||||