Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
ln(k 2 /T) -6.0 -7.5 -9.0 -10.5 -12.0 -13.5 -15.0 -16.5 -18.0 TU DMTU TMTU I SCN Br 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, (K -1 ) Figures S3.3: Temperature dependence of k2, M -1 s -1 , for the substitution of the chloride from CH3PhisoqPtCl, by thiourea nucleophiles I = 0.1 M (LiSO3CF3) in methanol. Table S3.2a: Average observed rate constants, kobs, s -1 , for substitution of chloride from pyPhenPtCl by thiourea nucleophiles, T = 298 K, I = 0.1 M (LiSO3CF3) TU (λ = 308 nm) DMTU (λ =370 nm) TMTU (λ = 339 nm) Conc., M kobs, s -1 0.0005 1.4628 6.88 x 10 -4 Conc., M kobs, s -1 31 0.5415 6.88 x 10 -4 Conc., M kobs, s -1 0.1032 0.001 3.3150 0.00138 1.1255 0.00138 0.1995 0.0015 5.2825 0.00206 1.7128 0.00206 0.2821 0.002 6.8256 0.00275 2.3766 0.00275 0.3885 0.0025 8.5872 0.00344 2.9588 0.00344 0.475
Table S3.2b: Average observed rate constants, kobs, s -1 , for substitution of chloride from pyPhenPtCl by ionic nucleophiles, T = 298 K, I = 0.1 M (LiSO3CF3). I - (λ = 308 nm) SCN - (λ =415 nm) Br - (λ = 339 nm) Conc., M kobs, s -1 3.675 x 10 -4 7.350 x 10 -4 Conc., M kobs, s -1 0.454 3.675 x 10 -4 0.946 7.350 x 10 -4 32 Conc., M kobs, s -1 0.06798 3.675 x 10 -4 0.12574 7.350 x 10 -4 0.0108 0.0216 0.00110 1.350 0.00110 0.18135 0.00110 0.0326 0.00147 1.708 0.00147 0.25052 0.00147 0.0432 0.00184 2.260 0.00184 0.30788 0.00184 0.0493 Table S3.3a: Average observed rate constants, kobs, s -1 , for substitution of chloride from CH3PhisoqPtCl by thiourea nucleophiles, T = 298 K, I = 0.1 M (LiSO3CF3). TU (λ = 363 nm) DMTU(λ = 363 nm) TMTU (λ = 386 nm) Conc., M kobs, s -1 2.679 x 10 -4 5.358 x 10 -4 8.037 x 10 -4 1.070 x 10 -3 1.340 x 10 -3 Conc., M kobs, s -1 0.1094 2.859 x 10 -4 0.2054 5.718 x10 -4 0.3053 8.577 x 10 -4 0.4003 1.140 x 10 -3 0.5003 1.430 x 10 -3 0.03674 5.5 x 10 -4 0.07474 1.0 x 10 -3 Conc., M kobs, s -1 0. 01532 0.03022 0.01100 1.5 x 10 -3 0.04530 0.14510 2.0 x 10 -3 0.18010 2.5 x 10 -3 0.06022 0.07541
- Page 86 and 87: Table 2.1: A selection of n o pt va
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Table S3.2b: Average observed rate constants, kobs, s -1 , for substitution <strong>of</strong> chloride from<br />
pyPhenPtCl by ionic nucleophiles, T = 298 K, I = 0.1 M (LiSO3CF3).<br />
I - (λ = 308 nm) SCN - (λ =415 nm) Br - (λ = 339 nm)<br />
Conc., M kobs, s -1<br />
3.675 x 10 -4<br />
7.350 x 10 -4<br />
Conc., M kobs, s -1<br />
0.454 3.675 x 10 -4<br />
0.946 7.350 x 10 -4<br />
32<br />
Conc., M kobs, s -1<br />
0.06798 3.675 x 10 -4<br />
0.12574 7.350 x 10 -4<br />
0.0108<br />
0.0216<br />
0.00110 1.350 0.00110 0.18135 0.00110 0.0326<br />
0.00147 1.708 0.00147 0.25052 0.00147 0.0432<br />
0.00184 2.260 0.00184 0.30788 0.00184 0.0493<br />
Table S3.3a: Average observed rate constants, kobs, s -1 , for substitution <strong>of</strong> chloride from<br />
CH3PhisoqPtCl by thiourea nucleophiles, T = 298 K, I = 0.1 M (LiSO3CF3).<br />
TU (λ = 363 nm) DMTU(λ = 363 nm) TMTU (λ = 386 nm)<br />
Conc., M kobs, s -1<br />
2.679 x 10 -4<br />
5.358 x 10 -4<br />
8.037 x 10 -4<br />
1.070 x 10 -3<br />
1.340 x 10 -3<br />
Conc., M kobs, s -1<br />
0.1094 2.859 x 10 -4<br />
0.2054 5.718 x10 -4<br />
0.3053 8.577 x 10 -4<br />
0.4003 1.140 x 10 -3<br />
0.5003 1.430 x 10 -3<br />
0.03674 5.5 x 10 -4<br />
0.07474 1.0 x 10 -3<br />
Conc., M kobs, s -1<br />
0. 01532<br />
0.03022<br />
0.01100 1.5 x 10 -3 0.04530<br />
0.14510 2.0 x 10 -3<br />
0.18010 2.5 x 10 -3<br />
0.06022<br />
0.07541
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