Search results for "PALLADIUM"

Mechanism of the palladium-catalysed electrosynthesis of diethyl carbonate from carbon monoxide and ethanol

2004

Abstract A mechanism is proposed for the PdBr2(PPh3)2-catalysed electrosynthesis of diethyl carbonate from carbon monoxide and ethanol, proceeding at room temperature and atmospheric CO pressure. The mechanism is investigated by cyclic voltammetry and 31P NMR spectroscopy. The active Pd0 complex able to coordinate CO is generated by the chemical reduction of PdBr2(PPh3)2 by EtO– ions generated from EtOH at the cathode. After reaction of EtO– ions with Pd0(PPh3)2(CO), the ensuing anionic complex [(PPh3)2Pd0–COOEt]– is oxidized at the anode in a key step leading to BrPdII–COOEt(PPh3)2. A nucleophilic attack of ethoxide on the latter generates diethyl carbonate and the Pd0 complex active in th…

Enantioselective Palladium-Catalyzed Oxidative β,β-Fluoroarylation of α,β-Unsaturated Carbonyl Derivatives

2016

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The site-selective palladium-catalyzed three-component coupling of deactivated alkenes, arylboronic acids, and N-fluorobenzenesulfonimide is disclosed herein. The developed methodology establishes a general, modular, and step-economical approach to the stereoselective β-fluorination of α,β-unsaturated systems.

Palladium-Catalyzed Alkoxy- and Aminocarbonylation of α-Halomethyl Oxime Ethers: Synthesis of 1,3-Alkoxyimino Esters and 1,3-Alkoxyimino Amides

2014

The three component reactions of α-bromomethyl oxime ethers, carbon monoxide, and alcohols or aromatic amines give imino esters and amides, respectively.

Potential anticancer heterometallic Fe-Au and Fe-Pd agents: Initial mechanistic insights

2013

A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenylphosphanes [{Cp-P(Ph2)═N-Ph}2Fe] (1), [{Cp-P(Ph2)═N-CH2-2-NC5H4}2Fe] (2), and [{Cp-P(Ph2)═N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)], and [{PdCl2}2(2)]. The complexes have been evaluated for their antiproliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a nontumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimeta…

Studies on atomic layer deposition of IRMOF-8 thin films

2015

Deposition of IRMOF-8 thin films by atomic layer deposition was studied at 260–320 C. Zinc acetate and 2,6-naphthalenedicarboxylic acid were used as the precursors. The as-deposited amorphous films were crystallized in 70% relative humidity at room temperature resulting in an unknown phase with a large unit cell. An autoclave with dimethylformamide as the solvent was used to recrystallize the films into IRMOF-8 as confirmed by grazing incidence x-ray diffraction. The films were further characterized by high temperature x-ray diffraction (HTXRD), field emission scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), time-of-flight elastic recoil detection analysis (TOF-…

Kinetic and equilibrium study for Pd(II) removal from aqueous solution by sorption onto calcium alginate gel beads

2013

The more and more increasing use of catalytic converters to reduce the dangerous NOx and CO emission in the atmosphere by vehicle traffic produces a corresponding increase of palladium in the environment [1]. Among the so-called “platinum group Elements” (PGE), elemental palladium seems to be the most hazardous one because it can be easily and quickly oxidized to palladium(II) when put in contact with soil. The presence of palladium oxidized form is of great concern owing to its recognized toxicity towards plants, animals and humans. Therefore, as for the classical “heavy metals”, a removal of this element from the environment is needed and a subsequent recovery for its potential re-use is …

Computational Investigation of Palladium Supported Boron Nitride Nanotube Catalysts

2015

A QM/MM investigation is reported dealing with the nucleation and growth of small palladium clusters, up to Pd8 , on the outer surface of a suitable model of boron nitride nanotube (BNNT). It is shown that the BNNT could have a template effect on the cluster growth, which is due to the interplay between Pd-N and Pd-Pd interactions as well as to the matching of the B3N3 ring and the Pd(111) face arrangement. The values for the clusters adsorption energies reveal a relatively strong physisorption, which suggests that in particular conditions the BNNTs could be used as supports for the preparation of shape-controlled metal cluster

DFT investigation of polyalcohols reforming on palladium cluster

2015

Biomass conversion technologies have recently gained high industrial interest for the production of sustainable fuels and fine chemicals; starting feedstocks for these processes are generally complex mixtures of oxygenated compounds, ranging from lignans, carbohydrates and polyalcohols to carboxylic acids [1]. Framed within this scientific context the entire reforming mechanism of two well-known polyols, namely ethylen glycol (C2) and glycerol (C3), on a small Pd cluster was investigated by means of density functional theory. Among the large amount of reaction pathways that can be followed in the reforming of oxygenates, we discuss here only the route that brings to carbon monoxide and hydr…

Studio teorico della reazione di idroisomerizzazione del cis-butene su cluster di palladio supportato

2008

LIQUIDI IONICI E FULLERENI: PIATTAFORME PER NUOVI MATERIALI

The synthesis of innovative catalysts based on different carbon nanoforms (CNFs), namely fullerene C60 and carbon nanotubes (CNTs), and their application in Suzuki and Heck C-C coupling reactions, constitutes the common thread of the first part (Chapter 1 and 2) of this thesis. C60 and CNTs were functionalized with ionic liquids (ILs) and poly-amidoamine (PAMAM) dendrimers, respectively, and used as supports for palladium nanoparticles (PdNPs). Moreover, additional supported catalytic systems based on one of the synthesized C60-IL hybrids were prepared and successfully employed in the title coupling reactions. The final part (Chapter 3) of the thesis deals on the microwave-mediated synthesi…