Tuning Reactivity of Platinum(II) Complexes

Figure 2.2 Potential energy profiles of the different mechanisms occurring at a
square-planar Pt(II) centre as proposed by Langford Gray …………4
Figure 2.3 Typical plots of the pseudo first-order rate constants, kobs vs. the
concentration of the entering nucleophiles for the substitution
reaction of a dinuclear Pt(II) complex at 298 K in
aqueous solution……………………………………………………………………...10
Figure 2.4 Summary of reaction techniques and their associated time scales
available for the monitoring chemical
kinetics…………………………………………………………………………………..17
Figure 2.5 A schematic diagram of a continuous flow kinetic system...............19
Figure 2.6 Schematic diagram of a stopped flow apparatus…………………….....20
Figure 2.7 Kinetic trace at 448 nm for the substitution reaction between
CH3PhisoqPtCl……..………………………………………………………………….20
Figure 2.8 Schematic diagram of a UV/Visible spectrophotometry set-up.....21
Figure 2.9 Rates of Pt(II) complexes correlated with trans-[Pt(py)2Cl2] as
reference, for different entering nucleophiles at 35 °C …………….27
Figure 2.10. The larger steric of the cis isomer in the trigonal Bipyramidal
intermediate in comparison to trans isomer ……….…………….……..32
Figure 2.11 Geometry of an aryl square-planar complex showing the ortho
substituents blocking the site of attack…………………..……….………..32
Figure 2.12 Schematic representation of π-back bonding of a π-acceptor
ligand …………………………………………………………………………………….37
Figure 3.1 DFT-calculated (B3LYP/LACVP**) HOMOs and LUMOs for polypyridyl
complexes…………………………………………………………….13
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