Abstract:
This thesis describes the synthesis of ruthenium complexes which contain
cyclopentadienyl ligands with electron-withdrawing ring substituents and the effects of
these substituents on the reactivity of the metal centre. Two metal complexes containing
the dibenzoylcyclopentadienyl ligand have been reported in the literature. However, the
effects of these substituents on the reactivities of the complexes have not been
investigated.
Several dibenzoylcyclopentadiene analogues react readily with triruthenium
dodecacarbonyl in toluene when heated under reflux to form bridging carbonyl dimeric
complexes. The metal¿metal bond in the dimers is cleaved upon reaction with halogen
sources. These halide complexes undergo CO substitution with tertiary phosphines. The
rate constants for the CO substitution reactions of the (n5-1,2-(COPh)2C5H3)Ru(CO)2X
complexes with tertiary phosphines have been measured.
Reaction rates for the parent cyclopentadienyl complexes, [RuCp(CO)2X], have been
repeated and the rates of the related indenyl complexes, [Ru(indenyl)(CO)2X], have been
measured for comparison.The electron withdrawing ring substituents activate the
complexes for CO substitution. The reaction mechanism is dissociative in all cases except
the [RuCp(CO)2I] which has an Id mechanism.
DFT calculations for second row transition metals are limited to 3-21G* basis sets.
However, they are able to reproduce new vMC-O stretching frequencies and atom
charges for the metal atoms which reflect the electron withdrawing effects of the ring
substituents.
