Tuning Reactivity of Platinum(II) Complexes

Figure 6.1 Spectrophotometric titration curve of Pt3 with NaOH in the pH
range 2-9, I = 1.0 M (NaClO4), T = 25 °C. Inset: plot of Absorbance
vs pH at 280 nm ……………..…………………………………………….………..10
Figure 6.2 DFT optimised structures of the dinuclear platinum (II)
complexes………………………………………………………………………………14
Figure 6.3 The 1H NMR spectra of the reaction of Pt1 with thiourea (2.0 mM)
in DMF-d7, at 30 °C showing the release of the dps bridging ligand
………………………………………………………………………………………………16
Figure 6.4 (a) Stopped-flow and (b) UV-Vis spectrophotometric curves for
Pt2 with TU at 305 nm, T = 298 K, I = 0.10 M (0.01 M HClO4,
adjusted with NaClO4), pH = 2.0 ……………..……………………...............18
Figure 6.5 Concentration dependence of kobs(1 st ) for the displacement of aqua
ligands in Pt1 by thiourea nucleophiles and ionic nucleophiles, pH
= 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with
NaClO4) …………………………………………………………………………………19
Figure 6.6 Concentration dependence of kobs(2nd) for the displacement of
bridging ligand in Pt1 by thiourea nucleophiles and ionic
nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4,
adjusted with NaClO4) ……………………………………………………………20
Figure 6.7 Plots of ln(k2(1 st )/T) versus (1/T) for the first step reaction of Pt1
with a series of different nucleophiles at varying temperatures
………………………………………………………………………………………………23
Figure 6.8 Plots of ln(k2(2 nd )/T) versus (1/T) for the second step reaction of
Pt1 with a series of different nucleophiles at varying
temperatures ……........................................................................................24
Figure 6.9 Schematic structures of Pt1 and free ligand illustrating the
twisted conformation of Pt1…………………………….……………….........27
xv