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
