Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
Table S4.23: Average observed rate constants, kobs(2 nd ), for the second step reactions of 2,3pzn at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [2,3pzn]. 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 6.932 x 10 -5 -10.1238 3.947 x 10 -4 -8.3844 4.218 x 10 -5 -10.6210 0.00341 1.041 x 10 -4 -9.7340 6,237 x 10 -4 -7.9440 6.521 x 10 -5 -10.2021 0.00335 1.578 x 10 -4 -9.3351 9.737 x 10 -4 -7.5155 1.084 x 10 -4 -9.7108 0.00330 2.070 x 10 -4 -9.0807 1.493 x 10 -3 -7.1050 1.526 x 10 -4 -9.3851 0.00325 3.313 x 10 -4 -8.6265 2.256 x 10 -3 -6.6500 2.109 x 10 -4 -9.0783 Table S4.24: Average observed rate constants, kobs(3 rd ), for the reactions of 2,3pzn at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [2,3pzn]. 1/T, K -1 TU DMTU TMTU kobs(3 rd ), s -1 ln(k2/T) kobs(3 rd ), s -1 ln(k2/T) kobs(3 rd ), s -1 ln(k2/T) 0.00347 1.823 x 10 -5 -11.4603 1.357 x 10 -5 -11.7546 6.486 x 10 -6 -12.4928 0.00341 2.509 x 10 -5 -11.1574 2.161 x 10 -5 -11.3065 1.065 x 10 -5 -12.0140 0.00335 3.643 x 10 -5 -10.8013 3.154 x 10 -5 -10.9454 1.547 x 10 -5 -11.6578 0.00330 4.984 x 10 -5 -10.5207 4.573 x 10 -5 -10.5906 2.139 x 10 -5 -11.3545 0.00325 7.257 x 10 -5 -10.1950 6.363 x 10 -5 -10.2765 3.243 x 10 -5 -10.9505 62
ln(k 2(1 st ) /T) -3.5 TU -4.0 -4.5 -5.0 -5.5 -6.0 -6.5 -7.0 -7.5 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 63 DMTU TMTU Figure S4.20: Graph of ln (k2/ T) versus (1/T) for first step of the reaction of 2,3pzn with a series of different nucleophiles at varying temperatures. ln(k nd 2(2 ) /T) -6.0 TU -6.5 -7.0 DMTU TMTU -7.5 -8.0 -8.5 -9.0 -9.5 -10.0 -10.5 -11.0 0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 Figure S4.21: Graph of ln (k2/ T) versus (1/T) for second step of the reaction of 2,3pzn with a series of different nucleophiles at varying temperatures.
- Page 158 and 159: Table 4.1: A summary of the DFT cal
- Page 160 and 161: H2O-Pt-L-Pt-OH2 H2O-Pt-L-Pt-OH2 H2O
- Page 162 and 163: electrophilicity and acidity of the
- Page 164 and 165: (A) 18 Absorbance 0.08 0.07 0.06 0.
- Page 166 and 167: k obs(3 rd ) , s -1 -5 6.00x10 TMTU
- Page 168 and 169: 4.3.4 Kinetics with NMR The substit
- 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
- Page 174 and 175: Comple x Table 4.4: Summary of Acti
- Page 176 and 177: The decrease in reactivity of 2,6pz
- 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
- Page 186 and 187: Appendix 4 THE INFLUENCE OF THE PYR
- Page 188 and 189: Absorbance at 368. 0 nm 0. 0 8 0. 0
- Page 190 and 191: Table S4.3: Average observed rate c
- Page 192 and 193: k nd obs(2 ) , s-1 0.003 TU DMTU TM
- Page 194 and 195: Table S4.7: Average observed rate c
- Page 196 and 197: Table S4.8: Average observed rate c
- Page 198 and 199: k obs2 , s -1 2.40x10 -4 2.20x10 -4
- Page 200 and 201: Table S4.13: Average observed rate
- Page 202 and 203: Table S4.14: Average observed rate
- Page 204 and 205: Table S4.18: Average observed rate
- Page 206 and 207: k obs(1 st ) , s -1 0.06 0.04 0.02
- Page 210 and 211: ln(k 2(3 rd ) /T) -10.0 -10.5 -11.0
- Page 212 and 213: SpinWorks 2.5: 2,6 pznClO4 in D2O N
- Page 214 and 215: Table of Contents-5 Chapter 5 .....
- Page 216 and 217: List of Tables Table 5.1: A summary
- Page 218 and 219: 5.1 Introduction Multinuclear plati
- Page 220 and 221: onding. For this reason, pKa titrat
- Page 222 and 223: 400-300 cm -1): 3308, 3117, 3071 (N
- Page 224 and 225: 5.2.6 Spectrophotometric pKa Titrat
- Page 226 and 227: Table 5.1: A summary of DFT-calcula
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- Page 232 and 233: Table 5.3: A summary of DFT calcula
- Page 234 and 235: H3N 6 eq TU 0 eq TU Ha NH3 Ha Cl TU
- Page 236 and 237: third step due to the trans-effect
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- Page 240 and 241: k obs(1st) / s -1 0.20 TU DMTU TMTU
- Page 242 and 243: thiourea nucleophile is large enoug
- Page 244 and 245: ln(k st 2(1 ) /T) -3 -4 -5 -6 -7 -8
- Page 246 and 247: is the same as the electron-withdra
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- Page 254 and 255: 276 nm Absorbance 0 . 6 5 0 . 6 4 0
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ln(k 2(1 st ) /T)<br />
-3.5 TU<br />
-4.0<br />
-4.5<br />
-5.0<br />
-5.5<br />
-6.0<br />
-6.5<br />
-7.0<br />
-7.5<br />
0.00325 0.00330 0.00335 0.00340 0.00345 0.00350<br />
1/T, K -1<br />
63<br />
DMTU<br />
TMTU<br />
Figure S4.20: Graph <strong>of</strong> ln (k2/ T) versus (1/T) for first step <strong>of</strong> the reaction <strong>of</strong> 2,3pzn<br />
with a series <strong>of</strong> different nucleophiles at varying temperatures.<br />
ln(k nd<br />
2(2 ) /T)<br />
-6.0 TU<br />
-6.5<br />
-7.0<br />
DMTU<br />
TMTU<br />
-7.5<br />
-8.0<br />
-8.5<br />
-9.0<br />
-9.5<br />
-10.0<br />
-10.5<br />
-11.0<br />
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350<br />
1/T, K -1<br />
Figure S4.21: Graph <strong>of</strong> ln (k2/ T) versus (1/T) for second step <strong>of</strong> the reaction <strong>of</strong> 2,3pzn<br />
with a series <strong>of</strong> different nucleophiles at varying temperatures.
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