Please use this identifier to cite or link to this item: http://hdl.handle.net/2067/1197
Title: Palladium and Gold Perfluoro-Tagged Phosphine-Free Nanoparticles and Bio-Palladium Nanoparticles: New Catalysts for Organic synthesis
Authors: Prastaro, Alessandro
Keywords: Nanocatalysis;Nanoparticles;Green chemistry;CHIM/06
Issue Date: 19-Feb-2009
Publisher: Università degli studi della Tuscia - Viterbo
Series/Report no.: Tesi di dottorato di ricerca 21. ciclo
Abstract: 
Solid-supported palladium-catalyzed reactions have become valuable tools for facilitating the recovery and reutilization of palladium and reducing the palladium contamination of the isolated products, a significant problem for the pharmaceutical industry. Activated carbon is the most commonly used insoluble support for palladium. Silica has also been used as an inert surface to adsorb palladium. A different approach to supported palladium catalysts involves the coordination of palladium to a ligand covalently bound to a polymer backbone. More recently, micro encapsulation of palladium in polymeric coating has been shown to be an efficient and cost effective technique to legate and retain palladium species and, in the same direction, aerogels, a new class of porous solids obtained via sol-gel processes coupled with supercritical drying of wet gels, have also been shown to exhibit a great potential for the preparation of heterogeneous catalysts.
In this thesis, was investigated the synthesis, growth and immobilization of phosphine-free perfluoro-tagged palladium and gold nanoparticles on fluorous silica gel (FSG). In order to establish a “tool box” for the synthesis of these supported catalysts, the study of several parameters such as the property of the support and the choice and the stability of the catalyst are necessary. To establish this set of rules, a limited number of catalytic transformations, were studied. These catalytic reactions are the Heck-Mizoroki, Suzuki-Miyaura and alkynylation Sonogashira-Heck-Cassar coupling and Oxidation reactions. These transformations became fundamental for the synthesis of drugs and materials. In the last part of this thesis was shown the green catalytic properties of an homogeneous bioinorganic catalyst. It was formed by palladium nanoparticles stabilizer by DPS-Te protein. This catalyst was tested on Suzuki cross-coupling reaction in water and in the one-pot synthesis of chiral biaryl alcohols through Suzuki- Miyaura cross-coupling and subsequent enzymatic reduction.

In questa tesi viene esaminata la sintesi, la crescita e l’immobilizzazione di nanoparticelle perfluorurate di palladio ed oro, immobilizzate su silice perfluorurata. Al fine di stabilire un ‘tool box’ per la sintesi di questi catalizzatori supportati, è necessario lo studio di alcuni parametri quali le proprietà del supporto e la stabilità del catalizzatore. Per verificare questo set di parametri, si è preso in considerazione un limitato numero di trasformazioni catalitiche. Queste sono le reazioni di Heck-Mizoroki, Suzuki-Miyaura, Sonogashira-Heck-Cassar cross-coupling e reazioni di ossidazione, fondamentali per la sintesi di alcuni farmaci e materiali. Nell’ultima parte di questa tesi sono state riportate le proprietà catalitiche di un nuovo tipo di catalizzatore bio-inorganico, formato da nanoparticelle di palladio stabilizzate dalla proteina DPS-Te. Questo catalizzatore è stato testato sulla reazione di Suzuki-Miyaura seguita da biotrasformazione.
Description: 
Dottorato di ricerca in Scienze ambientali
URI: http://hdl.handle.net/2067/1197
Rights: If not otherwise stated, this document is distributed by the Tuscia University Open Archive under a Creative Commons 2.0 Attribution - Noncommercial - Noderivs License (http://creativecommons.org/licenses/by-nc-nd/2.0/)
Appears in Collections:Archivio delle tesi di dottorato di ricerca

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