Towards an effective control of the electronic properties in Au(I)-complexes.
From basic principles to asymmetric catalysis.
dc.contributor.advisor | Alcarazo, Manuel Prof. Dr. | |
dc.contributor.author | González Fernández, Elisa | |
dc.date.accessioned | 2017-02-21T10:12:36Z | |
dc.date.available | 2017-02-21T10:12:36Z | |
dc.date.issued | 2017-02-21 | |
dc.identifier.uri | http://hdl.handle.net/11858/00-1735-0000-002B-7D54-E | |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-6129 | |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-6129 | |
dc.language.iso | eng | de |
dc.publisher | Niedersächsische Staats- und Universitätsbibliothek Göttingen | de |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | |
dc.subject.ddc | 540 | de |
dc.title | Towards an effective control of the electronic properties in Au(I)-complexes. | de |
dc.title.alternative | From basic principles to asymmetric catalysis. | de |
dc.type | doctoralThesis | de |
dc.contributor.referee | Alcarazo, Manuel Prof. Dr. | |
dc.date.examination | 2017-02-03 | |
dc.description.abstracteng | The 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 atom. | de |
dc.contributor.coReferee | Ackermann, Lutz Prof. Dr. | |
dc.contributor.thirdReferee | Höbartner, Claudia Prof. Dr. | |
dc.contributor.thirdReferee | Meyer, Franc Prof. Dr. | |
dc.contributor.thirdReferee | Stalke, Dietmar Prof. Dr. | |
dc.contributor.thirdReferee | Siewert, Inke Dr. | |
dc.subject.eng | carbenes | de |
dc.subject.eng | gold catalysis | de |
dc.subject.eng | enantioselective catalysis | de |
dc.subject.eng | helicenes | de |
dc.subject.eng | cationic phosphonites | de |
dc.identifier.urn | urn:nbn:de:gbv:7-11858/00-1735-0000-002B-7D54-E-2 | |
dc.affiliation.institute | Fakultät für Chemie | de |
dc.subject.gokfull | Chemie (PPN62138352X) | de |
dc.identifier.ppn | 880691557 |