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dc.contributor.advisorNolan, Steven P.
dc.contributor.authorPatrick, Scott R.
dc.description.abstractThe fields of N-heterocyclic carbenes and homogeneous gold catalysis have experienced tremendous growth within the last two decades. In addition, the combination of these fields to give NHC-gold complexes has delivered superior stability and reactivity, allowing the isolation of new reactive species and a better understanding of the fundamental chemistry. The work presented in this thesis attempts to synthesise novel NHC-gold complexes and document their reactivities. The main themes discussed in this work are: (a) the understanding and avoidance of silver additives in gold-mediated transformations; and (b) the study of different NHCs to provide optimal sterics and electronics for a given application. In Chapter 2, the reported “Gold(I)-Mediated C-H Activation of Arenes” is investigated. The role of each additive is assessed, and in particular the reliance on silver salts is considered. An NHC ligand was used to stabilise reactive intermediates, which provided new insights into the function of the silver additive. Gold(I) hydroxides are repeatedly shown to be invaluable synthetic equivalents, as well as key intermediates in silver-free protocols. Chapter 3 details numerous attempts to synthesise [Au(OH)(NHC)] complexes that are stable, pure and in high yields. Chapter 4 documents the synthesis of gold species featuring the ITent family of NHC ligands. Their highly flexible steric bulk is investigated by crystallographic studies, and is believed to contribute to their relatively high stabilities. Chapter 5 describes the use of the newly synthesised [Au(OH)(NHC)] complexes to generate mono- and bifluoride species. The reaction conditions were then optimised in order to maximise yields and regioselectivities. Finally, Chapter 6 examines the use of NHC selenium adducts to measure the π-accepting ability of these ligands. These are then coordinated to gold, whereupon different geometries are observed depending on the nature of the NHC.en_US
dc.publisherUniversity of St Andrews
dc.relation“Synthesis and Catalytic Applications of Mono- and Digold(I) Hydroxides,” Patrick, S. R.; Nolan, S. P., 2014, in preparationen_US
dc.relationPatrick, S. R.; Boogaerts, I. I. F.; Gaillard, S.; Slawin, A. M. Z.; Nolan, S. P., Beilstein J. Org. Chem. 2011, 7, 892en_US
dc.relationPatrick, S. R.; Gómez-Suárez, A.; Slawin, A. M. Z.; Nolan, S. P., Organometallics 2014, 33, 421en_US
dc.relationNahra, F.; Patrick, S. R.; Collado, A.; Nolan, S. P., Polyhedron 2014, DOI: 10.1016/j.poly.2014.06.017en_US
dc.relationPatrick, S. R.; Collado, A.; Meiries, S.; Slawin, A. M. Z.; Nolan, S. P., J. Organomet. Chem. 2014, DOI: DOI: 10.1016/j.jorganchem.2014.04.022en_US
dc.relationHydrofluorination of Alkynes Catalysed by Novel Au(NHC) Bifluorides,” Nahra, F.; Patrick, S. R.; Bello, D.; O’Hagan, D.; Nolan, S. P., 2014, in preparationen_US
dc.subject.lcshCarbenes (Methylene compounds)en_US
dc.subject.lcshGold compoundsen_US
dc.subject.lcshComplex compoundsen_US
dc.subject.lcshMetal catalystsen_US
dc.titleSynthesis and reactivity of novel (NHC)gold(I) complexesen_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 4th November 2021en_US

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