Coyle, Joanne Lyssa
Trigonal based copper sites - a natural situation?
The Open University.
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This thesis is concerned with the synthesis and characterisation of copper model compounds which are of interest in a biological context. These model compounds fall into two main classes; iminopodands and azacryptands. The iminopodands are derived from the condensation of tris(2- aminoethy1)amine (tren) or tris(3-aminoisopropy1)amine (trpn) and a range of aromatic aldehydes. The compounds invariably co-ordinated Cu(1) and the structural consequences of the flexibility are examined and systematised. Their redox properties have also been studied and correlated with their structure.
The main topic of this thesis concerns average valence dicopper cryptates. The synthesis has been studied in full including a description of likely decomposition and/or by-products. Considerable attention has been given to the spectroscopy of the average valence dicopper cryptates; Resonance Raman, ESRENTIOR and solution and solid state NMR have been described. Two additional properties which have been given serious attention are the redox chemistry and electron self exchange kinetics because of the relevance of these properties to the natural sites we are attempting to model i.e. the CuA site of cytochrome c oxidase.
In the final chapter preliminary experiments to synthesise a thiolate cryptand are reported in an attempt to model a S(cysteine) bridging function now known to exist in CuA.
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