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dc.contributor.advisorCazin, Catherine Suzanne Julienne
dc.contributor.authorLazreg, Faïma
dc.coverage.spatialxvi, 245 p.en_US
dc.description.abstractAs part of a worldwide effort to develop efficient catalysts for use in organic chemistry and in the synthesis of highly valuable molecules, work performed during the course of my stay in St Andrews has focused on the design and synthesis of new group 11 metal complexes for their applications in catalysis. The aim of this work was to develop new, active and stable, easy to synthesise group 11 complexes and investigate their catalytic activity as well as to try to understand their mode of action. Two different types of complexes were explored in order to develop more active catalysts: the neutral N-Heterocyclic carbene metal complexes and the cationic derivatives. More than 20 new catalysts were developed and their reactivity studied in different catalytic reactions. New hydroxide and tert-butoxide copper(I) or silver(I) complexes were developed and compared to the common NHC metal systems. Overall, the neutral NHC-metal catalysts showed to be highly active in a broad range of applications: in the methylation of amines using CO₂ as a C1 source, in a multicomponent reaction (A³ coupling) and in dual catalysis (hydrophenoxylation). Additionally, mechanistic studies were undertaken to obtain a greater understanding of these transformations and to possibly lead to the design of new generations of catalyst. Regarding the cationic NHC metal complexes, a straightforward methodology was developed leading to a library of highly stable catalysts. Bis-NHC, mixed NHC/phosphine as well as NHC/pyridine species were efficiently synthesised using thermal or microwave heating, in high purity and yields. In addition, the effect of the presence of two different or identical ligands on catalytic reactivity was investigated in the 3+2 cycloaddition and in the alkynylation of ketones. Insight into the catalytic cycle was obtained via mechanistic studies. These showcased the release of one ligand during the catalytic cycle and the crucial role of this ligand displacement in generating the catalytically relevant active species. The results highlight the importance of understanding the reactivity of catalyst in order to develop new and improved ones.en_US
dc.publisherUniversity of St Andrews
dc.rightsCreative Commons Attribution-NoDerivatives 4.0 International
dc.subjectN-heterocyclic carbeneen_US
dc.subject.lcshCarbenes (Methylene compounds)en_US
dc.subject.lcshComplex compoundsen_US
dc.subject.lcshCopper compoundsen_US
dc.subject.lcshSilver compoundsen_US
dc.subject.lcshMetal cataystsen_US
dc.titleGroup 11 N-heterocyclic carbenes : synthesis, characterisation and catalytic applicationsen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargoreasonThesis restricted in accordance with University regulations. Print and electronic copy restricted until 17th March 2022en_US

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Creative Commons Attribution-NoDerivatives 4.0 International
Except where otherwise noted within the work, this item's licence for re-use is described as Creative Commons Attribution-NoDerivatives 4.0 International