Tuning Reactivity of Platinum(II) Complexes

Figure 5.3: 1H NMR spectra of the reaction of cis-[{PtCl(NH3)2}2-μ-pzn] 2+ and excess
thiourea (TU). Charges omitted for clarity. ............................................................................................ 18
Figure 5.4: 1H NMR spectra of the reaction of cis-[{Pt(OH2)(NH3)2}2-μ-pdn]2+ and 20
fold excess thiourea (TU). ............................................................................................................................... 19
Figure 5.5: (a) Stopped-flow and (b) UV-Vis Spectrophotometric kinetic traces for the
reaction between qzn and TU recorded at 305 nm, T = 25 °C, I = 0.10 M (0.01 M HClO4,
adjusted with NaClO4), pH = 2.0. The inserts in (b) represent the substitution of the
second....................................................................................................................................................................... 21
Figure 5.6: Concentration dependence of kobs(1st) for the displacement of first aqua
ligand in pmn by thiourea and its substituted derivatives, pH = 2.0, T = 298.15 K, I = 0.10
M (0.01 M HClO4, adjusted with NaClO4). ................................................................................................ 24
Figure 5.7: Concentration dependence of kobs(2nd) for the displacement of second aqua
ligand in pmn by thiourea and its substituted derivatives, pH = 2.0, T = 298.15 K, I = 0.10
M (0.01 M HClO4, adjusted with NaClO4). ................................................................................................ 24
Figure 5.8: Concentration dependence of kobs(3rd) for the displacement of the bridging
ligand in pmn by thiourea and its substituted derivatives, pH = 2.0, T = 298.15 K, I = 0.10
M (0.01 M HClO4, adjusted with NaClO4). ................................................................................................ 25
Figure 5.9 : Plots of ln(k2/ T) versus 1/T for the first reaction step of pmn with a series
nucleophiles in the temperature range 15-35 °C, I = 0.10 M (0.01 M HClO4, adjusted
with NaClO4). ......................................................................................................................................................... 28
Figure 5.10: Plots of ln(k2/ T) versus 1/T for the second reaction step of pmn with a
series nucleophiles in the temperature range 15-35 °C, I = 0.10 M (0.01 M HClO4,
adjusted with NaClO4). ..................................................................................................................................... 28
Figure 5.11: Plots of ln(k2/ T) versus 1/T for the third reaction step of pmn with a series
nucleophiles in the temperature range 15-35 °C, I = 0.10 M (0.01 M HClO4, adjusted
with NaClO4). ......................................................................................................................................................... 29
ii