Show simple item record

Towards an effective control of the electronic properties in Au(I)-complexes.

From basic principles to asymmetric catalysis.

dc.contributor.advisorAlcarazo, Manuel Prof. Dr.
dc.contributor.authorGonzález Fernández, Elisa
dc.publisherNiedersächsische Staats- und Universitätsbibliothek Göttingende
dc.titleTowards an effective control of the electronic properties in Au(I)
dc.title.alternativeFrom basic principles to asymmetric
dc.contributor.refereeAlcarazo, Manuel Prof. Dr.
dc.description.abstractengThe dissertation is divided in two different parts, both related with gold(I) chemistry. In the first part, a new class of gold(I)-carbene complexes, the acyclic (amino)-(ylide)carbene (AAYCs) gold(I) chlorides, are presented together with a study of their reactivity. Their cyclic counterparts, (amino)-(ylide)carbenes, have been already reported as ligands to transition metals and present interesting properties, including an excellent σ-donor ability, keeping moderate π-acceptor attributes. Acyclic carbenes have significant stereoelectronic differences compared with cyclic scaffolds, together with the advantage of being easily accessible from the nucleophilic attack to certain metal-isonitrile complexes. Based on the synthesis of acyclic (diamino)carbene-gold(I) chlorides, we have developed a modular strategy for obtaining the AAYC-gold(I) chlorides through the nucleophilic attack of ylides to isonitrile-gold(I) chlorides. Moreover, the presence of additional functional groups on the carbenes side arm allowed their easy derivatisation, leading to the synthesis of heterobinuclear — bearing Rh(I) and Au(I) centres — and cationic AAYC-gold(I) complexes, together with an unprecedented Au(I)→Rh(III) and Au(I)→Ru(II) carbene transmetalation. In the second part of this thesis, TADDOL-based, α-cationic phosphonite ligands are developed and applied to the enantioselective synthesis of hexahelicene derivatives: helical, polyaromatic compounds with potential applications as ligands in asymmetric catalysis,liquid crystals with non-linear optical responses or molecular switches.The use of these novel class of cationic phosphonites as ancillary ligands allowed a highly regio- and enantioselective synthesis of substituted [6]-carbohelicenes through a sequential Au(I)-catalysed intramolecular hydroarylation of achiral diynes. Key for these results are the modular structure of the chiral, cationic phosphonites, and the enhanced reactivity that they impart to Au(I)-centres after coordination due to the presence of a positive charge adjacent to the phosphorus
dc.contributor.coRefereeAckermann, Lutz Prof. Dr.
dc.contributor.thirdRefereeHöbartner, Claudia Prof. Dr.
dc.contributor.thirdRefereeMeyer, Franc Prof. Dr.
dc.contributor.thirdRefereeStalke, Dietmar Prof. Dr.
dc.contributor.thirdRefereeSiewert, Inke Dr.
dc.subject.enggold catalysisde
dc.subject.engenantioselective catalysisde
dc.subject.engcationic phosphonitesde
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullChemie  (PPN62138352X)de

Files in this item


This item appears in the following Collection(s)

Show simple item record