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Title: Copper(I)-N-heterocyclic carbene (NHC) complexes : synthesis, characterisation and applications in synthesis and catalysis
Author: Santoro, Orlando
ISNI:       0000 0004 5917 1971
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2016
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The 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.
Supervisor: Cazin, Catherine Suzanne Julienne Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: N-heterocyclic carbenes ; Copper ; Catalysis ; Transmetallation ; Methylation ; CO2 ; QD305.H7S26 ; Carbenes (Methylene compounds) ; Copper compounds ; Complex compounds ; Metal catalysts