Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
k obs(3 rd ) , s -1 -5 6.00x10 TMTU DMTU TU 5.00x10 -5 4.00x10 -5 3.00x10 -5 2.00x10 -5 1.00x10 -5 0.00 0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 [NU]/ mol dm -3 Figure 4.7: Concentration dependence of kobs(3 rd ) for the release of bridging ligand in 2,5pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). The graphs indicate that in each step the reaction is first order with respect to nucleophile concentration. The slopes of the plot gave the second order rate constants (k1/2/3) in each step and the values are summarized in Table 4.3. 20
Table 4.3: Summary of second order rate constants for the substitution of coordinated aqua ligands and dissociation of the linker by thiourea nucleophiles in the [{cis-Pt(OH2)(NH3)2–μ–pzn] +4 complexes, I = 0.1 M (0.01 M HClO4, adjusted by NaClO4), T = 298.15 K H 3 N H 3N H 3 N H 3 N OH 2 Pt NH 3 OH 2 Pt NH 3 OH 2 Pt NH 3 OH 2 Pt NH 3 Complex NU k1/M -1 s -1 k2/M -1 s -1 k3/10 -3 M -1 s -1 NH 3 N N Pt pzn OH 2 N N Pt 2,6pzn NH 3 OH 2 N N Pt 2,3pzn NH 3 OH 2 N N Pt 2,5pzn NH 3 OH 2 4+ NH 3 4+ NH 3 4+ NH 3 4+ NH 3 TU DMTU TMTU TU DMTU TMTU TU DMTU TMTU TU DMTU TMTU 42.04 ± 0.56 22.46 ± 0.23 4.02 ± 0.06 8.13 ± 0.03 10.50 ± 0.24 3.53 ± 0.07 5.36 ± 0.10 2.14 ± 0.04 0.44 ± 0.001 4.39 ± 0.19 2.21 ± 0.06 0.41 ± 0.001 21 0.30 ± 0.01 0.15 ± 0.01 0.09 ± 0.0.003 0.06 ± 0.003 0.04 ± 0.003 0.01 ± 0.002 0.19 ± 0.0 0.17 ± 0.04 0.02 ± 0.01 0.19 ± 0.01 0.16 ± 0.01 0.015 ± 0.003 2.86 ± 0.07 3.65 ± 0.15 1.54 ± 0.10 7.89 ± 0.53 6.08 ± 0.10 2.73 ± 0.10 5.13 ± 0.01 1.81 ± 0.03 0.19 ± 0.003 7.29 ± 0.01 3.81 ± 0.04 0.20 ± 0.02 The linear regression plots had non-zero intercept for all the complexes, suggesting that little or no reverse reaction due to solvolysis or parallel reaction had occurred and the corresponding rate law can be given by Equation 4.1. kobs = k1/2/3 [NU] (4.1)
- Page 116 and 117: PhCN PhCN Pt Cl Cl + N N CH 3 N CH
- Page 118 and 119: Complex Structure HOMO LUMO PtCl CH
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- Page 124 and 125: Table 3.2: Summary of the second-or
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- Page 130 and 131: 3.6 References 1 D. Rosenberg, L. V
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- Page 138 and 139: Table S3.3b: Average observed rate
- Page 140 and 141: Table S3.5b: Temperature dependence
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- Page 182 and 183: References 1 T. Storr, K. H.Thomson
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k obs(3 rd ) , s -1<br />
-5<br />
6.00x10 TMTU<br />
DMTU<br />
TU<br />
5.00x10 -5<br />
4.00x10 -5<br />
3.00x10 -5<br />
2.00x10 -5<br />
1.00x10 -5<br />
0.00<br />
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009<br />
[NU]/ mol dm -3<br />
Figure 4.7: Concentration dependence <strong>of</strong> kobs(3 rd ) for the release <strong>of</strong><br />
bridging ligand in 2,5pzn by thiourea nucleophiles, pH = 2.0,<br />
T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4).<br />
The graphs indicate that in each step the reaction is first order with respect to<br />
nucleophile concentration. The slopes <strong>of</strong> the plot gave the second order rate constants<br />
(k1/2/3) in each step and the values are summarized in Table 4.3.<br />
20
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