Research into inorganic supramolecular chemistry is burgeoning, in
particular that which focuses on the formation of capsular molecules and the
effects that these unique environments have on catalytic reactions. With the
aim of producing new ligand designs that could not only support reactive
metals, but also partake in supramolecular aggregation to provide a capsular
microenvironment, new tripodal ligands and wide span imines and amines
have been synthesised. Furthermore, the exploitation of hydrogen-bonding
motifs formed through pyrrole-imine tautomerisation upon metallation of
these ligands has been explored, with the aim of enhancing reactivity and
stabilising reactive intermediates.
In Chapter one, the concept of covalent and non-covalent capsules is
introduced, and includes the different aspects affecting the encapsulation of
molecules and their use as nanoreactors. The use of secondary interactions,
e.g. hydrogen-bonding in metal complexes of tetrapodal and tripodal ligands
is discussed.
Chapter two describes the synthesis of a tripodal pyrrole-imine ligand
and the formation of its multi-metallic complexes of Group one metals,
transition metal and the f-block elements. The complete and partial
tautomerisation of this ligand upon metal complexation is also examined.
In Chapter three, the formation of hangman complexes of the tripodal
pyrrole-imine ligand is described and is extrapolated to the chemistry of a
new pyrrole-amide ligand. The synthesis of this latter ligand and its
properties with regards to anion binding are also explored.
Chapter four describes the formation of wide span diamine and
diimine ligands and their propensity to form adducts with cobalt and zinc
chlorometallates and unusual multimetallic palladium complexes.
The final conclusions of the work presented in this thesis are drawn in
Chapter five.
Chapter six presents experimental details and characterising data for
all of the new compounds presented in this thesis