Show simple item record

Files in this item


There are no files associated with this item.

Item metadata

dc.contributor.advisorCazin, Catherine Suzanne Julienne
dc.contributor.authorSantoro, Orlando
dc.coverage.spatialxii, 175 p.en_US
dc.description.abstractThe work described herein focuses on the synthesis and characterisation of copper(I) complexes bearing N-heterocyclic carbene (NHC) ligands, their use in catalysis as well as organometallic synthesis and related reaction mechanisms. Two classes of complexes were considered: neutral NHC-Cu(I) species and their cationic analogues. Concerning the former, initial efforts were focused on the development of a general and straightforward synthetic methodology towards complexes of the type [Cu(X)(NHC)] (X = Cl, Br, I). More than 10 NHC-Cu(I) species were synthesised in high yields under mild conditions, in air and using technical grade solvents. These complexes exhibited interesting activity in the catalytic dehydrogenation of formic acid/amine adducts proving in three times more efficiency than the copper salts previously employed in such a reaction. Hydroxide- and tert-butoxide analogues showed to be efficient catalysts in the N-methylation of amines with CO₂ as carbon source, and in the dehydrogenative coupling of silanes and carboxylic acids. Experimental and computational work were carried out in order to elucidate the mechanism of these transformations. Regarding the use of these species in organometallic synthesis, homo- and heteroleptic bis-NHC-Cu(I) complexes were employed as carbene transfer reagents to other transition metals. Aside from well-known cationic gold(I) species, two novel palladium(II) analogues were isolated and fully characterised.en_US
dc.publisherUniversity of St Andrews
dc.rightsCreative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
dc.subjectN-heterocyclic carbenesen_US
dc.subject.lcshCarbenes (Methylene compounds)en_US
dc.subject.lcshCopper compoundsen_US
dc.subject.lcshComplex compoundsen_US
dc.subject.lcshMetal catalystsen_US
dc.titleCopper(I)-N-heterocyclic carbene (NHC) complexes : synthesis, characterisation and applications in synthesis and catalysisen_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 2nd March 2023en_US

The following licence files are associated with this item:

  • Creative Commons

This item appears in the following Collection(s)

Show simple item record

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