Search results for " Catalyst"

Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing

2021

Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclohexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto’s catalyst), are widely used organocatalysts with virtually unknown environmental safety data. Ecotoxicity studies based on the Vibrio fischeri luminescence inhibition test reveal significant toxicity of Takemoto’s catalyst (EC50 = 7.9 mg/L) and its NH2-substituted analog (EC50 = 7.2–7.4 mg/L). The observed toxic effect was pronounced by the influence of the trifluoromethyl moiety. En route to the porphyrin-based chemosensing of Takemoto-type thioureas, their s…

Multidentate Tetrahydrofurfuryloxide Ligand in a Ziegler−Natta Catalyst Studied by Molecular Modeling

2008

The transition from a generation III Ziegler-Natta catalyst with a monodentate Lewis base to a more modem generation 1V/V system, containing a tetrahydrofuran derivative, the tetrahydrofurturyloxide C 4 H 7 O-CH 2 O - bidentate ligand (THFFO), was studied by means of molecular modeling and DFT calculations. This particular ligand was carefully chosen so that it remained in the titanium coordination sphere in the model active site. With such a constraint, the dual role of tetrahydrofurfuryloxide was identified: it was demonstrated how the presence of this ligand limits the number of isomeric active sites as well as enhances the selectivity of the species that can still exist. The results ind…

ChemInform Abstract: Switchable Palladium-Catalyst Reaction of Bromomethyl Sulfoxides, CO, and N-Nucleophiles: Aminocarbonylation at Csp3versus Oxida…

2013

Pd2(dba)3/ Xantphos-catalyzed coupling of the sulfoxides (I) and (V) with amines and carbon monoxide allows a new and efficient access to amides of type (IV) and (VI).

POSS-Al-porphyrin-imidazolium cross-linked network as catalytic bifunctional platform for the conversion of CO2 with epoxides

2023

Two heterogeneous catalysts were prepared with the aim of following the promising path of CO2 fixation into epoxides. The synthetic procedure involves a radical copolymerization of an octavinylsilsesquioxane as inorganic core building block and tetrastyrylporphyrin aluminum chloride monomer (TSP-AlCl) in presence (POSS-TSP-AlCl-imiBr) or in absence (POSS-TSP-AlCl) of a bis-vinylimidazolium bromide salt (bis-imiBr), in order to investigate if the bifunctional heterogeneous material can display better catalytic performance than the separate species. All the solids were fully characterized and tested in the synthesis of cyclic carbonates starting from CO2 and several epoxides. The synergic coo…

Enantiocontrol in the intermolecular cyclopropanation reaction catalyzed by dirhodium(II) complexes with ortho-metalated aryl phosphine ligands

2001

(P) and (M) dirhodium(II) complexes with ortho-metalated aryl phosphines are assessed as chiral catalysts in the enantioselective cyclopropanation of styrenes by ethyl diazoacetate; enantioselectivities up to 91% and up to 87%, respectively, for cis- and trans-2-arylcyclopropanecarboxylates are observed. Barberis, Mario, Mario.Barberis@uv.es ; Lahuerta Peña, Pascual, Pascual.lahuerta@uv.es ; Perez Prieto, Julia, Julia.Perez@uv.es ; Sanau Torrecilla, Mercedes, Mercedes.Sanau@uv.es

DFT analysis of titanium complexes with oxygen-containing bidentate ligands

2003

Strength of the TiO co-ordinate bond in several titanium complexes with bidentate ligands has been investigated by means of DFT. Mutual interaction of particular donors and their influence on Lewis acidity of the central atom have also been studied. The energy of ligand binding ranges from −19 to −454 kJ/mol, depending on the kind of donors. Calculations confirm that a strong donor, alkoxide anion, co-ordinatively saturates the titanium and makes binding of new ligands less exoenergetic. On the contrary, two oxygen atoms of similar donor number do not have much influence on each other. Strength of the TiO bonds in titanium complexes with certain oxygen-containing bidentate ligands has bee…

Theoretical study of isomerism in phenoxyimine-based precursors of coordinative olefin polymerization catalysts

2010

Precursors of post-metallocene olefin polymerization catalysts, unlike their predecessors, are usually octahedral transition metal complexes with multidentate ligands. Such ligands may wrap around the central atom in many ways, thus yielding several isomeric species. For a wide range of phenoxyimine (FI) ligands with different substituents, all the theoretically predicted diastereomers of group 4 and 5 complexes are available synthetically. However, only one of the isomers is usually preferred, and this is determined by the nature of the substituents in the FI ligand. The origin and mechanism of such preference has not been completely elucidated. We attempted to describe it quantitatively o…

Pd nanoparticles immobilized on the poly-dopamine decorated halloysite nanotubes hybridized with N-doped porous carbon monolayer: A versatile catalys…

2020

A hybrid catalyst, Pd@Hal-pDA-NPC, with the utility for promoting both C–C coupling reactions (Sonogashira, Heck and Suzuki reactions) and hydrogenation of nitrocompounds is prepared through two main steps. First, Pd(0) nanoparticles was immobilized on the poly-dopamine decorated halloysite nanotubes (Hal-pDA) and then Pd@Hal-pDA was hybridized with the layers of a novel multi-N-doped porous carbon monolayer derived from 4,4′,4″-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzonitrile. The results established that the catalyst could catalyze all the reactions efficiently under mild reaction condition. Moreover Pd@Hal-pDA-NPC exhibited high recyclability (up to ten reac…

Synthesis, Characterization, and Study, of New Nanostructured Materials

EFFICIENT DEGRADATION OF CLOFIBRIC ACID BY HETEROGENEOUS PHOTOCATALYTIC OXIDATION PROCESS

2019

International audience; Emerging pollutants such as pharmaceutical active compounds were detected worldwide in different environmental compartments. Nowadays, multiple studies are focused on the investigation of their environmental fate, as well as to find new, efficient and sustainable removal technologies. Several studies demonstrated that heterogeneous photocatalysis is one of the most promising techniques used for water purification. Thus, the aim of our work was to evaluate the photodegradation efficiency of a refractory emergent compound, named clofibric acid, under UV light in aqueous solution. We report that photodegradation and mineralization efficiency are strongly dependent of th…