Studies towards the synthesis of fused N-Heterocyclic carbene precursors
Degree GrantorUniversity of Canterbury
Degree NameMaster of Science
This thesis describes the preparation of a various NHC ligands with five and six-membered rings, different fused aromatic cores and the subsequent synthetic development of their complexation of with Ag, Ru and Pd. The investigation and preparation of these compunds was with the intention of exploring their chemical and physical properties. The synthesis of the NHC ligands proved to be difficult, but analysis and characterisation of the side products from the reactions helped to establish successful synthetic methodologies. In both the five and six-membered research conducted a common attribute was established of a pyrid-2-yl substituent at the 1 position or both the 1 and 3 positions, thus providing new NHC ligands to investigate. The organic syntheis of the research focused on two NHC ligand functionalites, five and six membered rings. The six memerbered rings focused on 1H-perimidine as the core unit and the design of both bidentate and tridentate NHC ligands to mimic the structural binding relationship of 2,2’- bipyridine (bpy) and 2,2’:6’2”-terpyridine (tpy) with various metal salts. The synthesis of the bpy analogues was achieved in good overall yields with minimal synthetic challenges. However, the tpy analogue was unable to be realised due to time constraints and problems associated with its synthesis. The five membered NHC ligands synthesised were to investigate the physical effects of systematically increasing the size of its aromatic core. The main focus of the research was on the phenanthrene imidazole NHC ligands. This was investigated due to the minimal research that has been conducted on this core unit and NHC-complexes. Synthesis of the two-bidentate NHC ligands with an imidazole head group and fused phenanthrene backbone were completed, but this was with a picolyl substituent at the 1 position rather than the pyrid-2-yl substituent. This failure to isolate this product was attributed to steric influences. Pyrene-fused-imidazole NHC ligands were also investigated and pyrene offers a NHC core that hasn’t been investigated previously. However, synthesis and isolation of the NHC ligands proved to be difficult and was associated with the poor solubility of the NHC ligands. The organometallic NHC synthesis was studied extensively with the main focus on establishing appropriate conditions to give a NHC complex. The main metal investigated was ruthenium as subsequent NHC complexes were expected to have potentially interesting properties such as luminescence. The synthesis of a perimidine and phenanthrene NHC ruthenium complexes have not been isolated before, thus giving new NHC complexes. Many different synthetic routes were attempted to synthesise a perimidine NHC ruthenium complex. However, this proved difficult due to associated higher reactivity of the carbene carbon of perimidine with a new side product as a result of this research. The phenanthrene NHC complex synthesis suffered due to time constraints but potential methodology for their synthesis is stated.