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Very Active Catalysts (very + active_catalyst)
Selected AbstractsStable and Catalytically Highly Active ansa Compounds with Cycloalkyl Moieties as Bridging UnitsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Alejandro Capapé Abstract The complexes Mo{,5 -C5H4[CH(CH2)3]-,1 -CH}(CO)3 (2a) and W{,5 -C5H4[CH(CH2)3]-,1 -CH}CO)3 (2b) were synthesized by reacting spiro[4.2]bicyclo[4.1]deca-6,8-diene (1) with the tri(acetonitrile)tri(carbonyl)metal complexes M(CO)3(CH3CN)3 (M=Mo, W). Thermogravimetric (TGA) measurements confirm that the complexes are stable up to 140,°C in air in the solid state. The complexes 2a and 2b are very active catalysts at room temperature for the epoxidation of cyclooctene with tert -butyl hydroperoxide (TBHP) as oxidant, reaching TOFs of up to 3650,h,1. Complex 2a achieves a quantitative product yield without formation of any by-products within 1.5,h, outperforming previously published ansa compounds and performing on par with the cyclopentadienyltri(carbonyl)(halo)- or (alkyl)molybdenum compelxes CpMo(CO)3R (R=Hal, Me, Et). [source] Studies of ethylene,styrene copolymerization with dinuclear constrained geometry complexes with methyl substitution at the five-membered ring in indenyl of [Ti(,5:,1 -C9H5SiMe2NCMe3)]2 [CH2]nJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2004Seok Kyun Noh Abstract The new dinuclear half-sandwich CGC (constrained geometry catalyst) with methyl substitution in indenyl, [Ti(,5:,1 -2-methylindenyl)SiMe2NCMe3]2 [(CH2)n] [n = 6 (10), n = 9 (11), n = 12 (12)], have been synthesized, and structure of these complexes has been characterized by 1H and 13C NMR. The most important feature is that two protons of methylene directly bonded to the indenyl ring become inequivalent to be shown as two separated resonances at 2.9 and 3.0 ppm, probably due to the formation of planar chirality caused by a titanium complex formation. It has been found that the dinuclear CGCs with methyl substitution at an indenyl ring were very active catalysts for ethylene and styrene copolymerization. The activity increases in the order of 10 < 11 < 12, which indicates that the presence of a longer bridge between two active sites contributes to facilitate the polymerization activity of the dinuclear CGC more effectively. This result might be understood by the implication that the steric factor rather than the electronic factor may play a major role to direct the polymerization behavior of the dinuclear CGC. It is found that the dinuclear catalysts are very efficient to incorporate styrene in the polyethylene backbone. The styrene contents in the formed copolymers ranged from 5 to 40% according to the polymerization conditions. One can observe strong signals at 29.7 ppm of the polyethylene sequences, and, in addition, peaks at 27.5, 36.9, and 46. 2ppm (S,,, S,,, and T,,, respectively) of sequences of EESEE. Weak peak at 25.3 ppm are attributed to S,,, which represents SES sequence. The absence of a signal for T,, at 41.3 ppm and for S,, at 43.6 ppm shows there is no styrene,styrene sequences in copolymers. This result indicates that the dinuclear CGC are very effective to generate well-distributed poly(ethylene- co -styrene)s. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1712,1723, 2004 [source] A simplified method for limit conversion calculation in membrane reactorsASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 1 2010Fausto Gallucci Abstract Membrane reactors (MRs) are often used to carry out equilibrium limited reactions. This is because the thermodynamic equilibrium is a strong constrain for traditional systems. Even with very active catalysts, traditional reactors (TRs) cannot give conversions higher than those allowed by the thermodynamic equilibrium. On the contrary, MRs are able to shift the equilibrium of a traditional system owing to the removal of at least one reaction product that takes place simultaneously to the reaction. In this work, a simplified method for the calculation of limit conversion in MR is discussed and compared with literature methods. The typical method for calculating equilibrium conversions in TR is also discussed. It has been demonstrated that the simplified method applied to two reaction systems gives fast predictions of the limit conversion for MR. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Phosphine Ligands in the Palladium-Catalysed Methoxycarbonylation of Ethene: Insights into the Catalytic Cycle through an HP,NMR Spectroscopic StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 23 2010Verónica de, la Fuente Dipl.-Chem. Abstract Novel cis -1,2-bis(di- tert -butyl-phosphinomethyl) carbocyclic ligands 6,9 have been prepared and the corresponding palladium complexes [Pd(O3SCH3)(L-L)][O3SCH3] (L- L=diphosphine) 32,35 synthesised and characterised by NMR spectroscopy and X-ray diffraction. These diphosphine ligands give very active catalysts for the palladium-catalysed methoxycarbonylation of ethene. The activity varies with the size of the carbocyclic backbone, ligands 7 and 9, containing four- and six-membered ring backbones giving more active systems. The acid used as co-catalyst has a strong influence on the activity, with excess trifluoroacetic acid affording the highest conversion, whereas excess methyl sulfonic acid inhibits the catalytic system. An in operando NMR spectroscopic mechanistic study has established the catalytic cycle and resting state of the catalyst under operating reaction conditions. Although the catalysis follows the hydride pathway, the resting state is shown to be the hydride precursor complex [Pd(O3SCH3)(L- L)][O3SCH3], which demonstrates that an isolable/detectable hydride complex is not a prerequisite for this mechanism. [source] | ||||||||||