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Title: Late transition metal complexes of NHC-based macrocycles
Author: Andrew, Rhiann E.
ISNI:       0000 0004 6062 4421
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2016
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N-heterocyclic carbene (NHC) ligands are an important and diverse ligand class, conferring stability and enabling reaction control of coordinated metal centres. Pincer ligand architectures bearing such donors are an increasingly prevalent design motif, combining the strong donor characteristics of carbenes with the favourable thermal stability possible with a mer-tridentate geometry. Macrocyclic variants of NHC-based pincers are of interest as they may impart further stability and reaction control, in addition to serving as potential building blocks for the construction of interlocked, supramolecular systems. Enabling study of the reactivity and structural properties of late transition metal complexes of macrocyclic CNC pincer ligands, the coordination chemistry of a series of pro-ligands of varying ring size (n = 1; m = 8, 10, 12) has been explored. Investigation of the dynamics and structures of palladium(II) halide complexes identified an optimal ring size, which was subsequently employed in the preparation of rhodium-based derivatives (n = 0, 1; m = 12) via two converging synthetic routes. The organometallic chemistry, dynamic behaviour and structures of the resulting rhodium complexes are described. Through investigation of terminal alkyne coupling reactions using a macrocyclic rhodium ethylene complex, potential for the preparation of novel supramolecular assemblies was explored. As a result, a series of complexes bearing mechanically entrapped enynes were isolated and fully characterised in solution and the solid-state.
Supervisor: Not available Sponsor: University of Warwick
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry