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Identifier 000443006
Title Εφαρμογές νανοσωματιδίων μετάλλων και μεταλλοοργανικών σκελετών στην ετερογενή κατάλυση οργανικών μετασχηματισμών
Alternative Title Applications of metal nanoparticles and metal organic frameworks in the heterogenous catalysis of organic transformations
Author Λουκά, Αναστασία Α
Thesis advisor Στρατάκης, Εμμανουήλ
Reviewer Βασιλικογιαννάκης, Γεώργιος
Τρικαλίτης, Παντελής
Σμόνου, Ιουλία
Νεοχωρίτης, Κωνσταντίνος
Λυκάκης, Ιωάννης
Βουγιουκαλάκης, Γεώργιος
Abstract In the present thesis were studied new applications of gold and palladium nanoparticles as catalysts on a variety of organic transformations, as well as preliminary studies regarding the CO2 fixation on epoxides catalyzed by a Zr-metal organic framework. In the First Chapter is described the superior reactivity of a dihydrosilane (diethylsilane), as compared to monohydrosilanes, towards a series of reductive transformations catalyzed by Au nanoparticles supported on TiO2. Furthermore, an unprecedented method for the synthesis of N-arylisoindolines is also shown. The exceptional reductive ability of diethylsilane is ascribed to the formation of reactive Au-dihydrides on the surface of the nanoparticle. In the Second Chapter, the Au nanoparticle-catalyzed activation of the Ge-H and Ge-Ge bonds of hydrogermanes and digermanes and their accompanying addition to alkynes and allenes forming vinylgermanes is reported for the first time in the literature. Additionally, the results regarding the Pd nanoparticle-catalyzed C-C coupling of 1,2-digermyl alkenes with aryl iodides are provided. In the Third Chapter, the deoxygenation of epoxides catalyzed by Au nanoparticles using a digermane as the oxygen atom acceptor is presented for the first time in the literature. The reaction is selective for mono- and di-substituted epoxides. Moreover, stereoisotopic and kinetic studies showed that the deoxygenation of alkyl epoxides takes place with retention of stereochemistry, whilst in the case of aryl epoxides partial inversion is observed, indicative of a polar mechnism In the Fourth Chapter, preliminary mechanistic studies of the CO2 fixation reaction with epoxides catalyzed by a Zr MOF (PCN-521) forming cyclic carbonates are presented. However, it is crucial that more experiments are yet to be carried out in order to extract confirmed mechanistic conclusions.
Language Greek
Subject Alkynes
C-C coupling
C-C σύζευξη
CO2 fixation on epoxides
Cyclic carbonates
Gold nanoparticles
Metalorganic frameworks
Reductive amination
Αναγωγική αμίνωση
Κυκλικοί ανθρακικοί εστέρες
Μεταλλοοργανικοί σκελετοί
Νανοσωματίδια χρυσού
Σύζευξη CO2 με εποξείδια
Issue date 2021-11-02
Collection   School/Department--School of Sciences and Engineering--Department of Chemistry--Doctoral theses
  Type of Work--Doctoral theses
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