Tuning Reactivity of Platinum(II) Complexes

and thermodynamic properties of mono- and dinuclear Pt(II) complexes. In this thesis
the kinetic behaviour of mono- and dinuclear Pt(II) complexes have been explored with
neutral ligands: thiourea, N,N-dimethylthiourea and N,N,N,N-tetramethylthiourea
and/or anions, bromide, iodide and thiocyanate. To help explain the kinetic trends and
determine how the structures of the complexes would influence reactivity of the Pt(II)
centres, Chemical Quantum calculations of the optimised complexes were performed
using DFT computation technique at the B3LYP/LACVP level of theory.
Specific Objectives of this study were:
1. To investigate the role of extended π-conjugation on substitution behaviour of
tridentate N-donor Pt(II) complexes in which one or two of the outer pyridine
rings of the terpy structure was converted into an isoquinoyl moiety
(specifically 4'-(2"'-CH3-phenyl)-6-(3’’-isoquinoyl)-2,2’-bipyridine) or a
phenanthroline moiety (2-(2’-pyridyl)-1,10-phenanthroline) as illustrated in
Figure 1.10. The results obtained were compared with those of the [Pt(2,2’-
terpyridine)Cl] + complex in literature. 103
N
3
Y
2
N
Pt
Cl
N
1
Figure 1.10: Structure of extended terpy Pt(II) complexes; blue ring for isoquinoline
ring and red for phenanthroline ring system.
2. To investigate the influence of position of bulky methyl groups on the σ-donor
and steric properties of pyrazine-bridged Pt(II) complexes; their effect on
kinetic and thermodynamic behaviour.
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