Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
k nd obs(2 ) , s-1 0.003 TU DMTU TMTU 0.002 0.001 0.000 0.00 0.02 0.04 0.06 0.08 0.10 [NU]/ mol dm -3 Figure S4.6: Concentration dependence of kobs(2 nd ) for the displacement of second water k obs , s-1 4.00x10 -5 3.50x10 -5 3.00x10 -5 2.50x10 -5 2.00x10 -5 1.50x10 -5 1.00x10 -5 5.00x10 -6 ligand in pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). TU DMTU TMTU 0.00 0.00 0.02 0.04 0.06 0.08 0.10 [NU]/ mol dm -3 Figure S4.7: Concentration dependence of kobs(3 rd ) for the displacement of second water ligand in pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). 46
Table S4.5: Average observed rate constants, kobs(1 st ), for the reactions of pzn at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [pzn]. 1/T, K -1 TU DMTU TMTU kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) 0.00347 0.08503 -5.3143 0.0332 -6.2548 0.0118 -7.2892 0.00341 0.1201 -4.9862 0.0468 -5.9286 0.0172 -6.9296 0.00335 0.1666 -4.6758 0.0671 -5.5853 0.0235 -6.6344 0.00330 0.2224 -4.4036 0.0911 -5.2961 0.0324 -6.3299 0.00325 0.2985 -4.1257 0.1253 -4.9737 0.0409 -6.1133 Table S4.6: Average observed rate constants, kobs(2 nd ), for the second step reactions of pzn at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [pzn]. 1/T, K -1 TU DMTU TMTU kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) 0.00347 7.626 x 10 -4 -10.028 3.707 x 10 -4 -10.750 5.376 x 10 -5 -12.681 0.00341 1.079 x 10 -3 -9.698 6.237 x 10 -4 -10.247 6.521 x 10 -5 -12.505 0.00335 1.692 x 10 -3 -9.266 1.022 x 10 -3 -9.770 7.691 x 10 -5 -12.357 0.00330 2.133 x 10 -3 -9.051 1.585 x 10 -3 -9.347 9.343 x 10 -5 -12.179 0.00325 3.697 x 10 -3 -8.519 2.391 x 10 -3 -8.953 1.105 x 10 -4 -12.027 47
- Page 142 and 143: Table S3.8: DFT calculated electros
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- Page 150 and 151: cis geometry, leading to dramatic c
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- Page 154 and 155: spectra were measured in and refere
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- Page 160 and 161: H2O-Pt-L-Pt-OH2 H2O-Pt-L-Pt-OH2 H2O
- Page 162 and 163: electrophilicity and acidity of the
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- Page 170 and 171: ln([ML] t ) 4.0 3.5 3.0 2.5 2.0 1.5
- Page 172 and 173: ln(k 2(1 st ) /T) -3.5 -4.0 -4.5 -5
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- Page 178 and 179: Table 4.5: DFT calculated (NBO) cha
- Page 180 and 181: eaction proceeds via bimolecular pa
- Page 182 and 183: References 1 T. Storr, K. H.Thomson
- Page 184 and 185: 36 D. Jaganyi, D. Reddy, J.A. Gerte
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Table S4.5: Average observed rate constants, kobs(1 st ), for the reactions <strong>of</strong> pzn at varied<br />
temperatures in the range 15 to 35 °C while maintaining nucleophile<br />
concentration at ≈ 60x [pzn].<br />
1/T, K -1 TU DMTU TMTU<br />
kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T)<br />
0.00347 0.08503 -5.3143 0.0332 -6.2548 0.0118 -7.2892<br />
0.00341 0.1201 -4.9862 0.0468 -5.9286 0.0172 -6.9296<br />
0.00335 0.1666 -4.6758 0.0671 -5.5853 0.0235 -6.6344<br />
0.00330 0.2224 -4.4036 0.0911 -5.2961 0.0324 -6.3299<br />
0.00325 0.2985 -4.1257 0.1253 -4.9737 0.0409 -6.1133<br />
Table S4.6: Average observed rate constants, kobs(2 nd ), for the second step reactions <strong>of</strong><br />
pzn at varied temperatures in the range 15 to 35 °C while maintaining<br />
nucleophile concentration at ≈ 60x [pzn].<br />
1/T, K -1 TU DMTU TMTU<br />
kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T)<br />
0.00347 7.626 x 10 -4 -10.028 3.707 x 10 -4 -10.750 5.376 x 10 -5 -12.681<br />
0.00341 1.079 x 10 -3 -9.698 6.237 x 10 -4 -10.247 6.521 x 10 -5 -12.505<br />
0.00335 1.692 x 10 -3 -9.266 1.022 x 10 -3 -9.770 7.691 x 10 -5 -12.357<br />
0.00330 2.133 x 10 -3 -9.051 1.585 x 10 -3 -9.347 9.343 x 10 -5 -12.179<br />
0.00325 3.697 x 10 -3 -8.519 2.391 x 10 -3 -8.953 1.105 x 10 -4 -12.027<br />
47
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