Search results for " Catalyst"

Kompleksy metali przejściowych z zasadami Lewisa jako prekursory katalizatorów polimeryzacji olefin. Cz. I. Postęp w komputerowym modelowaniu procesu…

2001

A review with 35 references covering molecular modeling in coordination polymerization over homogeneous and heterogeneous Ziegler-Natta catalysts. The study includes supports, cocatalysts, Lewis bases and solvents. Recent progress in elucidating the mechanisrn of elementary polymerization steps is presented against the background of rapidly deveIoping computational methods and available computational power. Theoretical studies on polymerization mcchanisms and structure of active centers are described (egns. 1-4). Authors own calculations are used to compare [MtC14(THF)2] complex-based (Mt = Ti, Hf or Zr) heterogeneous catalysts. The geometrical characteristics of precursors is presented (Ta…

Halloysite Nanotubes as Support for Metal-Based Catalysts

Halloysite nanotubes (HNTs) are a natural, biocompatible, environmental friendly and cheap double-layered aluminosilicate mineral that has a predominantly hollow tubular structure. The general stoichiometry of halloysite is Al2Si2O5·4(H2O). The layer units consist of a tetrahedral SiOH sheet stacked with an edge shared octahedral AlO6 sheet with an internal aluminol group AlOH. A water layer exists between the adjacent two layers. Thanks to their structural features, HNTs are suitable for a potential application as support for catalytic composites. Recently, we reported the synthesis of novel palladium-based catalytic systems using halloysite nanotubes modified with imidazolium or triazoliu…

GREEN CONDITIONS FOR THE SUZUKI REACTIONS BY USING MICROWAVE IRRADIATION AND MODIFIED HALLOYSITE/Pd CATALYST

2014

Halloysite nanotube (HNT) is an emerging biocompatible material with appealing perspective for technological applications, such as in catalysis1 and in pharmaceutical research.2 Halloysite is a double-layered aluminosilicate mineral that has a predominantly hollow tubular structure. The functionalization of HNTs is a good strategy to introduce an organic moiety onto the external surface and, therefore, to obtain innovative catalyst supports.3 We have modified the external surface of halloysite nanotube with octylimidazolium moieties (HNT-IL) by microwave irradiation in solvent-free conditions and we have have employed this material as support catalyst of Pd nanoparticles. The new HNT/Pd cat…

SYNTHESIS AND EVALUATION OF CATALYTIC ACTIVITY IN WATER AND MICROWAVE IRRADIATION OF A NEW SUPPORT BASED ON HNT TRIAZOLIUM SALTS

2014

In the last years SILLP (supported ionic liquid-like phase)-based materials prepared by covalent attachment have been synthesized [1]. Recently, we have synthesized a palladium-based catalytic system using halloysite nanotubes modified with octylimidazolium moieties and we have tested it in the Suzuki cross-coupling reaction under traditional heating, microwave irradiation and a very small amount of Pd catalyst [2,3]. It is known that support based on triazole motif showed superior activity to the analogous imidazole molecules [4] so, we have focused our attention to develop a new SILLP system with triazolium moiety. Herein we report the synthesis of an original Pd-dicationic triazolium sup…

Cross-Linked Imidazolium Salts as Scavengers for Palladium.

2014

Five imidazolium-based materials have been synthesised and used for the first time as palladium scavengers. Radical reactions of suitable bis-vinylimidazolium salts led to a series of insoluble materials through homo-polymerisation, immobilisation with a 3-mercaptopropyl-modified silica gel or co-polymerisation with ethylene glycol dimethylacrylate. These materials were screened as palladium scavengers with a set of palladium(0) and palladium(II) compounds in different solvents and at different starting amounts of palladium. In many cases, residual amounts of palladium were lower than 5 ppm, as requested for the manufacture of active pharmaceutical ingredients and fine chemicals. The applic…

Dual stereocontrolled alkylation of aldehydes with polystyrene-supported nickel complexes derived from α-amino amides

2015

Nickel(II) complexes derived from α-amino amide ligands anchored to gel-type and monolithic polymers act as efficient catalysts for the enantioselective addition of dialkylzinc reagents to aldehydes. Similar to the analogous homogeneous systems, dual stereocontrol in addition products can be achieved by controlling the stoichiometry of the immobilized nickel complex. Aromatic and aliphatic aldehydes were alkylated in good yields with enantioselectivities comparable to those obtained with the homogeneous analogues. These polymer-supported catalysts offer significant advantages as no metal leaching is observed and they can be easily recovered from the reaction mixture by simple filtration and…

Vanadium-based Ziegler-Natta catalyst supported on MgCl2(THF)2 for ethylene polymerization

1996

A supported magnesium‐vanadium‐aluminium catalyst was prepared by depositing –with the use of a milling technique–VOCl3 on the MgCl2(THF)2 support and subsequent activation with diethylaluminium chloride. Catalytic activity of the obtained system for ethylene polymerization was evaluated as a function of Mg/V and Al/V ratios as well as catalyst ageing time and polymerization temperature. High concentrations of THF in the catalytic system and considerable excess of an organoaluminium co‐catalyst were found to have no deactivating action on vanadium active sites. The catalyst obtained is stable and its activity for ethylene polymerization is high. It yields polyethylene with higher molecular …

Iron(iii) oxamato-catalyzed epoxidation of alkenes by dioxygen and pivalaldehyde

1997

A new iron(III)–carbonato monomeric complex of orthophenylenebis( oxamato) (opba) 1 is synthesized, and spectroscopically and structurally characterized; it is a moderately efficient non-heme catalyst for the aerobic epoxidation of alkenes with co-oxidation of pivalaldehyde. Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Fernandez Picot, Isabel, Isabel.Fernandez@uv.es ; Pedro Llinares, Jose Ramon, Jose.R.Pedro@uv.es

Oxidative dehydrogenation of ethane: A study over the structure and robustness of Ni–W–O catalysts

2014

[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the cata…

“Release and catch” catalytic systems

2013

In this perspective article the “release and catch” catalytic system concept is discussed. A “release and catch” catalytic system is prepared by non-covalent immobilization of the catalytic moiety on a suitable support, but differently from the usual non-covalently supported catalyst, the catalytic moiety is released in solution over the course of the reaction and it is recaptured at the end of the reaction. Such a “catalyst- sponge like” or “boomerang” system allows one to combine the benefits of homogeneous and heterogeneous catalysis and can be applied to organometallic-based catalysts, organocatalysts and metal-based catalysts.