Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
276 nm Absorbance 0 . 6 5 0 . 6 4 0 . 6 3 0 . 6 2 0 . 6 1 0 . 6 0 0 . 5 9 0 2 4 6 8 10 1 2 Figure S5.1: UV/Visible spectra for the titration of 0.1 mM pzn with NaOH in the pH range 2-11, T = 25° C. Inset is the titration curve at 276 nm. Table S5.2: Average observed rate constants, kobs(1 st ), at 298.15 K, for the reactions of pzn with a series of nucleophiles at different concentrations. [NU]/ M kobs(1), s -1 TU DMTU TMTU 0.02 0.0689 0,0444 0.0081 0.04 0.1681 0.0863 0.0164 0.06 0.2571 0.1337 0.0241 0.08 0.3434 0.1784 0.0321 0.1 0.4232 0.2217 0.0398 38 p H
Table S5.3: Average observed rate constants, kobs(2 nd), at 298.15 K, for the reactions of pzn with a series of nucleophiles at different concentrations. [NU]/M kobs(2), s -1 TU DMTU TMTU 0.02 5.543 x 10 -4 2.873 x 10 -4 1.889 x 10 -4 0.04 1.120 x 10 -3 6.239 x 10 -4 3.959 x 10 -4 0.06 1,710 x 10 -3 9.470 x 10 -4 5.294 x 10 -4 0.08 2.300 x 10 -3 1.280 x 10 -3 0.1 2.870 x 10 -3 1.620 x 10 -3 9.805 x 10 -4 Table S5.4: Average observed rate constants, kobs(3 rd ), at 298.15 K, for the reactions of pzn with a series of nucleophiles at different concentrations [NU]/ M kobs(3 rd ), (x10 -5 s -1) TU DMTU TMTU 0.02 0.4065 - 0.3578 0.04 1.1172 1.2512 0.7180 0.06 1.6147 2.0745 1.1125 0.08 2.3859 2.9302 1.5227 0.1 2.8822 3.7350 1.8200 39
- 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 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
- Page 228 and 229: However, because the highest occupi
- 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 256 and 257: k obs(1 st ) , s -1 0.4 0.3 0.2 0.1
- Page 258 and 259: Table S5.5: Average observed rate c
- Page 260 and 261: ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0
- Page 262 and 263: pzn PPM -1750.0 -1850.0 -1950.0 -20
- Page 264 and 265: Table S5.9: Average observed rate c
- Page 266 and 267: Figure S5.13: UV/Visible spectra fo
- Page 268 and 269: k obs(1 st ) in s -1 0.030 0.025 0.
- Page 270 and 271: Table S5.17: Average observed rate
- Page 272 and 273: ln(k 2(2 nd ) /T) -10 -11 -12 -13 -
- Page 274 and 275: 9.61 ppm Ha PPM 9.8 9.6 9.4 9.2 9.0
- Page 276 and 277: Table S5.22: Average observed rate
- Page 278 and 279: k obs(3rd) / s -1 -5 8 .00 x 10 T U
- Page 280 and 281: ln(k st 2(1 ) /T) -1.5 TU DMTU TMTU
- Page 282 and 283: ln(k rd 2(3 ) /T) -8.5 -9.0 -9.5 -1
- Page 284 and 285: SpinWorks 2.5: znPt(II)-OP4 in D2O
- Page 286 and 287: Figure S5.31: Mass spectrum for com
- Page 288 and 289: Table S5.28: Average observed rate
- Page 290 and 291: Table S5.29: Average observed rate
- Page 292 and 293: ln(k st 2(1 ) /T) -4 -5 -6 -7 -8 -9
- Page 294 and 295: SpinWorks 2.5: phtPt(II)-OP2 in D2O
- Page 296 and 297: Figure S5.41: Mass spectrum for com
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- Page 300 and 301: Chapter 6 Tuning Reactivity of Plat
- Page 302 and 303: Against this background, several re
276 nm<br />
Absorbance<br />
0 . 6 5<br />
0 . 6 4<br />
0 . 6 3<br />
0 . 6 2<br />
0 . 6 1<br />
0 . 6 0<br />
0 . 5 9<br />
0 2 4 6 8 10 1 2<br />
Figure S5.1: UV/Visible spectra for the titration <strong>of</strong> 0.1 mM pzn with NaOH in the pH<br />
range 2-11, T = 25° C. Inset is the titration curve at 276 nm.<br />
Table S5.2: Average observed rate constants, kobs(1 st ), at 298.15 K, for the reactions <strong>of</strong><br />
pzn with a series <strong>of</strong> nucleophiles at different concentrations.<br />
[NU]/ M kobs(1), s -1<br />
TU DMTU TMTU<br />
0.02 0.0689 0,0444 0.0081<br />
0.04 0.1681 0.0863 0.0164<br />
0.06 0.2571 0.1337 0.0241<br />
0.08 0.3434 0.1784 0.0321<br />
0.1 0.4232 0.2217 0.0398<br />
38<br />
p H
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