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Title: Coordination chemistry of N-heterocyclic carbene and thione functionalised calix[4]arene ligands
Author: Patchett, Ruth
ISNI:       0000 0004 6348 5789
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2016
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This thesis is a summary of the work carried out exploring the properties and applications of calix[4]arene ligands. Particular attention is given to the flexibility and encapsulation capabilities of these species. Initially synthetic methodology for the incorporation of bisimidazolinium and imidaolium groups was targeted. The synthesis of imidazolinium functionalised species proved problematic, however pro-ligand 2a-2HI was readily prepared via a six-step synthetic procedure. The coordination chemistry of 2a-2HI with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2, via generation of the free carbene (2a) or transmetallation from an isolated silver complex (6a) was explored. Both routes resulted in the formation of bimetallic species. The isolation of these complexes highlights the flexibility of the calix[4]arene scaffold. The role of the calix[4]arene was probed though comparison to complexes of the monodentate IiPr2Me2 ligand. Based on these results, the imidazole-2-thione (NHCS) ligand 3 was derived from 2a and elemental sulfur. Monodentate rhodium and iridium complexes of 3 were readily prepared and found to bind potassium cations within the calix[4]arene cavity. This unusual host-guest chemistry was probed by 1H NMR spectroscopy and in the solid state through comparison to other calix[4]arene hosts.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry