Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
k obs(1 st ) , s -1 0.06 0.04 0.02 0.00 TU DMTU TMTU 0.000 0.002 0.004 0.006 0.008 0.010 [NU]/ mol dm -3 Figure S4.17: Concentration dependence of kobs(1 st ) for the displacement of first aqua ligand in 2,3pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). k obs(2 nd ) in S -1 0.003 TU DMTU TMTU 0.002 0.001 0.000 0.000 0.002 0.004 0.006 0.008 [NU]/ mol dm -3 Figure S4.18: Concentration dependence of kobs(1 st ) for the displacement of first aqua ligand in 2,3pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). 60
k obs(3 rd ) in s -1 1.0x10 -4 8.0x10 -5 6.0x10 -5 4.0x10 -5 2.0x10 -5 0.0 TU DMTU TMTU 0.000 0.004 0.008 0.012 0.016 0.020 [NU]/ mol dm -3 Figure S4.19: Concentration dependence of kobs(3 rd ) for the displacement of linker in 2,3pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). Table S4.22: Average observed rate constants, kobs(1 st ), for the first 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(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 0.01113 -5.0451 5.104 x 10 -3 -5.8247 1.4165 x 10 -3 -7.1065 0.00341 0.01570 -4.7183 7.192 x 10 -3 -5.4990 1.9177 x 10 -3 -6.7413 0.00335 0.02167 -4.4129 0.01011 -5.1753 2.6020 x 10 -3 -6.5488 0.00330 0.03145 -4.0571 0.01332 -4.9162 3.1454 x 10 -3 -6.3595 0.00325 0.04456 -3.7250 0.01766 -4.6506 4.2479 x 10 -3 -6.0754 61
- Page 156 and 157: 4.3.1 DFT calculated Optimized Stru
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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
- 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 208 and 209: Table S4.23: Average observed rate
- 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 230 and 231: Table 5.2: Acid dissociation consta
- 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
- Page 238 and 239: [H 2 O-Pt-(NN)-Pt-OH 2 ] +4 [NU-Pt-
- 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
- Page 248 and 249: associative mode of substitution me
- Page 250 and 251: 16 H. Ertürk, J. Maigut, R. Puchta
- Page 252 and 253: 43 (a) D. Jaganyi, A. Hofmann and R
- Page 254 and 255: 276 nm Absorbance 0 . 6 5 0 . 6 4 0
k obs(3 rd ) in s -1<br />
1.0x10 -4<br />
8.0x10 -5<br />
6.0x10 -5<br />
4.0x10 -5<br />
2.0x10 -5<br />
0.0<br />
TU<br />
DMTU<br />
TMTU<br />
0.000 0.004 0.008 0.012 0.016 0.020<br />
[NU]/ mol dm -3<br />
Figure S4.19: Concentration dependence <strong>of</strong> kobs(3 rd ) for the displacement <strong>of</strong> linker in<br />
2,3pzn by thiourea nucleophiles, pH = 2.0, T = 298.15 K, I = 0.10 M (0.01<br />
M HClO4, adjusted with NaClO4).<br />
Table S4.22: Average observed rate constants, kobs(1 st ), for the first step reactions <strong>of</strong><br />
2,3pzn at varied temperatures in the range 15 to 35 °C while<br />
maintaining nucleophile concentration at ≈ 60x [2,3pzn].<br />
1/T, K -1 TU DMTU TMTU<br />
kobs(1 st ), s -<br />
1<br />
ln(k2/T) kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T)<br />
0.00347 0.01113 -5.0451 5.104 x 10 -3 -5.8247 1.4165 x 10 -3 -7.1065<br />
0.00341 0.01570 -4.7183 7.192 x 10 -3 -5.4990 1.9177 x 10 -3 -6.7413<br />
0.00335 0.02167 -4.4129 0.01011 -5.1753 2.6020 x 10 -3 -6.5488<br />
0.00330 0.03145 -4.0571 0.01332 -4.9162 3.1454 x 10 -3 -6.3595<br />
0.00325 0.04456 -3.7250 0.01766 -4.6506 4.2479 x 10 -3 -6.0754<br />
61
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