In this thesis, the chemistry of lanthanide and actinide complexes of Schiff-base, polypyrrolic macrocyclic ligands has been evaluated. Chapter one introduces some general chemistry of uranium before focussing on uranium(III) and (IV) coordination complexes of nitrogen donor ligands. The surface chemistry of uranium metal is also briefly discussed along with the synthesis of uranium borohydride, hydride and alkyl complexes. Chapter two describes the synthesis and characterisation of the monometallic complexes [M(L)] or [M(HL)], where M = Y, Ce, and U, of the octadentate Schiffbase pyrrole macrocycle H4L. In particular, these complexes display a new binding mode of the macrocycle which leads to the formation of the unique trinuclear supramolecular complexes [M(HL)]3, (M = Ce, Y). Reactions of these materials towards hydrolysis, oxygen sources and other metal reagents are also exemplified. Chapter three details the synthesis and characterisation of the bimetallic complexes, [(MX)2(L)], where M = Ce, U, and Np and X = I or Cl, and [(MX2)2(L)], where M = U, and the attempts to transform these complexes into metal hydrides via their borohydrides. The solid state variable temperature magnetism of the binuclear U(III) and Np(III) complexes was recorded and was found to be consistent with the formation of iodide-bridged, polymeric structures. Chapter four explores the synthesis and reactions of adducts between UI3 and neutral macrocyclic ligands that incorporate either oxygen or nitrogen donors such as crown ethers and cyclam, respectively. The new synthesis of the key starting material, unsolvated UI3 is also outlined, along with the full characterisation of UI4(OEt)2.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:630203 |
| Date | January 2011 |
| Creators | Potter, Natalie Alison |
| Contributors | Love, Jason; Arnold, Polly |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/9562 |
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