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Identifier

000397426

Title

Υδροσιλυλίωση αλλενίων καταλυόμενη από Au/TiO2

Alternative Title

Hydrosilylation of allenes catalyzed by Au/TiO2

Author

Κυδωνάκης, Μάριος Α.

Thesis advisor

Στρατάκης, Μανώλης

Reviewer

Ορφανόπουλος, Μιχαήλ
Βασιλικογιαννάκης, Γεώργιος

Abstract

In this dissertation we present the first methodology for the hydrosilylation of allenes based on the activation of σ Si-H bond by supported gold nanoparticles (Au NPs). It was found that the reaction is highly regioselective favoring the addition of hydrosilane on the more substituted double bond of a terminal allene (1,2-addition). The observed regioselectivity is attributed to steric and electronic factors. Mechanistic studies are in agreement with the development of a partial carbocation in the rate determining step (rds) and the formation of a π-allyl type intermediate. The use of a cyclopropyl substituted allene as a mechanistic probe led to rearrangend hydrosilylation products, which proves the existance of the intermediate. It was also found that the catalyst was 100% recyclable and reusable but most importantly no external additives or ligands are required.

Language

Greek

Subject

Au nanoparticles

Catalysis

Regioselectivity

Αλλένια

Κατάλυση

Νανοσωματίδια Au

Τοποεκλεκτικότητα

Issue date

2015-11-20