Highest Catalytic Activity (highest + catalytic_activity)

Distribution by Scientific Domains


Selected Abstracts


Neutral Group-IV Metal Catalysts for the Intramolecular Hydroamination of Alkenes

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2008
Carsten Müller
Abstract A detailed comparison of the group-IV metal catalysts Ti(NMe2)4, Ind2TiMe2, Ind2ZrMe2 and Ind2HfMe2 in the intramolecular hydroamination of amino alkenes is presented. Among these catalysts, the benchmark catalyst Ti(NMe2)4 is the most active in the formation of pyrrolidines. A comparison between Ind2TiMe2, Ind2ZrMe2 and Ind2HfMe2 suggests that in the synthesis of pyrrolidines, Zr complexes show the highest catalytic activity of the group-IV metal catalysts. Although Ind2TiMe2 - and the Ind2ZrMe2 -catalyzed formation of a pyrrolidine is first-order in the concentration of the substrate, the corresponding Ti(NMe2)4 -catalyzed cyclization is second-order in the concentration of the substrate. The results obtained for the formation of piperidines catalyzed by Ti(NMe2)4, Ind2TiMe2, Ind2ZrMe2 and Ind2HfMe2 suggest that for these reactions, Ti catalysts show increased catalytic activity compared with the corresponding Zr catalysts. Unfortunately, the formation of aminocyclopentane side-products by C,H activation processes is a severe drawback of the Ti catalysts. The corresponding side-products are not formed in Ind2ZrMe2 - and Ind2HfMe2 -catalyzed reactions. However, the former catalyst gives better yields of the desired piperidine products. In contrast to the results obtained for the synthesis of pyrrolidines, the formation of a piperidine is zero-order in the concentration of the substrate for the indenyl catalysts Ind2TiMe2 and Ind2ZrMe2, and first-order for the homoleptic catalyst Ti(NMe2)4. Interestingly, Ind2TiMe2 is able to catalyze a slow hydroamination of an N -methylated amino alkene, whereas the homoleptic complex Ti(NMe2)4 as well as Ind2ZrMe2 and Ind2HfMe2 do not catalyze the same reaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]


Polymerization of styrene with a simple rare earth metal initiator

POLYMER INTERNATIONAL, Issue 11 2001
Toshiyuki Hayakawa
Abstract The catalytic activity in the polymerization of styrene has been examined using commercially available simple rare earth metal compounds such as Sm(OiPr)3, Sm(acac)3, Sm(OCOMe)3, SmI2(THF)2 or SmCl3 coupled with Et3Al or methylaluminoxane (MAO). Among these compounds, the Sm(OiPr)3/AlEt3 system shows the highest catalytic activity, especially in the presence of a minor amount of toluene at 60,°C. The random copolymerization of styrene with methyl methacrylate suggests that the present polymerization proceeds with a radical polymerization mechanism. (C5Me5)SmCl3Na(THF) and (C5Me5)SmCl3Li(THF) systems exhibit relatively low catalytic activity, even in the presence of AlEt3. © 2001 Society of Chemical Industry [source]


Hydrogenation of naphthalene on nickel phosphide supported on silica

ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2009
Xiaofei Zhang
Abstract Two series of silica supported nickel phosphide catalysts with different Ni/P atomic ratios of the precursors and loadings had been prepared by a temperature-programmed reduction of nickel phosphate. The resulting samples were characterized by means of N2 physorption and X-ray diffraction (XRD). The activities of the catalysts were measured for naphthalene hydrogenation (HYD) at 340 °C and 4 MPa. The operating conditions of naphthalene HYD such as temperature, pressure and H2/liquor ratio were tested in detail. It is found that all the samples were active in this reaction and the sample which precursor with Ni/P = 1.25 and loading with 30 wt% displayed the highest catalytic activity and decalin selectivity. Naphthalene conversion and selectivity to decalin went through a maximum (100% and 83% at 340 °C) with the increasing reaction temperature. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source]


Glycerol Etherification over Highly Active CaO-Based Materials: New Mechanistic Aspects and Related Colloidal Particle Formation

CHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2008
Agnieszka
Abstract Glycerol is an attractive renewable building block for the synthesis of di- and triglycerols, which have numerous applications in the cosmetic and pharmaceutical industries. In this work, the selective etherification of glycerol to di- and triglycerol was studied in the presence of alkaline earth metal oxides and the data are compared with those obtained with Na2CO3 as a homogeneous catalyst. It was found that glycerol conversion increased with increasing catalyst basicity; that is, the conversion increases in the order: MgO90,% at 60,% conversion) are obtained over CaO, SrO, and BaO. For these catalysts no substantial acrolein formation was observed. Furthermore, at the start of the reaction mainly linear diglycerol was produced, whereas at higher conversion degrees branched diglycerol started to form. In another series of experiments different types of CaO materials were prepared. It was found that these CaO-based materials not only differed in their surface area and number of basic sites, but also in their Lewis acid strength. Within this series the CaO material possessing the strongest Lewis acid sites had the highest catalytic activity, comparable to that of BaO, pointing towards the important role of Lewis acidity for this etherification reaction. Based on these observations a plausible alternative reaction scheme for glycerol etherification is presented, which considers the facilitation of the hydroxyl leaving process. Finally, the stability of the catalytic solids under study was investigated and it was found that colloidal CaO particles of about 50,100,nm can be spontaneously generated during reaction. Catalytic testing of these CaO colloids, after isolation from the reaction medium, revealed a very high etherification activity. Understanding the nature of these Ca-based colloids opens new opportunities for investigating supported colloidal particle catalysts to take advantage of both their hetero- and homogeneous nature. [source]