|dc.contributor.author||Wells, Jordann Ashley Logan Slovenne Denis||
|dc.description.abstract||The work described in this thesis concerns the synthesis of actinide complexes and their reactivity
towards small unsaturated molecules. Complexes bearing tetraphenoxide, borohydride and
boroxide ligands have been evaluated. Additionally, work towards the synthesis of heterobimetallic
uranium transition metal complexes and their applications in catalysis is discussed.
Chapter one reviews important organoactinide complexes reported in the literature which
effect chemical transformations on small unsaturated substrates. Actinide complexes supported
by aryloxide or borohydride ligands are reviewed, along with actinide complexes in which metal
p-arene interactions are present.
Chapter two reports the synthesis and characterisation of a set of tetraphenol ligands,
in addition to a number of attempted synthetic routes to tetraphenol ligands with alternate
substitution. The chemistry of those tetradentate aryloxide ligands is introduced with bimetallic
uranium(IV) and thorium(IV) complexes using different An(IV) and U(III) precursors.
Chapter three reports the synthesis and characterisation of monometallic uranium and
thorium complexes using a tetraphenol ligand. The varying chemistry between the two similar
An(IV) ions, where the uranium complexes exist as a mixture of oligomers and the thorium
complexes remain as well defined mononuclear complexes, is discussed within. A range of base
adducts of mononuclear actinide complexes are reported, including a thorium trimethylsilylazide
complex, a rare example of a metal organoazide.
Chapter four describes the synthesis of homoleptic boroxide and heteroleptic borohydride
complexes of uranium(III). The reactivities of these complexes with small unsaturated molecules
are assessed, including the reaction of a low coordinate uranium(III) boroxide complex towards
CO2 to provide a dinuclear uranium carbonate bridged complex.
Chapter five introduces work towards heterobimetallic uranium transition metal complexes
carried out in the Arnold group. The application of these complexes towards ring opening
polymerisation chemistry is discussed in addition to investigations into the incorporation of
transition metals into uranium(IV) complexes.
Chapter Six presents the detailed experimental methods used to carry out this research.||en
|dc.publisher||The University of Edinburgh||en
|dc.relation.hasversion||Dinuclear uranium complexation and manipulation using robust tetraaryloxides Jordann A. L. Wells, Megan L. Seymour, Markéta Suvova and Polly L. Arnold Dalton Transactions, 2016, 45, 16026-16032||en
|dc.relation.hasversion||Uranium rhodium bonding in heterometallic complexes Johann A. Hlina, Jordann A. L. Wells, James R. Pankhurst, Jason B. Love and Polly L. Arnold Dalton Transactions, 2017, 46, 5540-5545||en
|dc.relation.hasversion||Ring opening polymerisation of lactide with uranium(IV) and cerium(IV) phosphinoaryloxide complexes Fern Sinclair, Johann A. Hlina, Jordann A. L. Wells, Michael P. Shaver and Polly L. Arnold Dalton Transactions, 2017, 46, 10786-10790||en
|dc.title||Bimetallic actinide complexes for small molecule activation||en
|dc.type||Thesis or Dissertation||en
|dc.type.qualificationname||PhD Doctor of Philosophy||en