Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
ln(k rd 2(3 ) /T) -8.5 -9.0 -9.5 -10.0 -10.5 -11.0 TMTU DMTU TU -11.5 0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 Figure S5.27: Plots of ln(k2/T) versus (1/T) for the third step reaction of qzn with a series of different nucleophiles at varying temperatures. 66
SpinWorks 2.5: znPt(II)-OP3 in D2O Ha 0.998 10.16 ppm 0.837 Hb 10.05 ppm 0.844 9.53 ppm Hf 67 8.50 ppm 8.38 ppm 8.11 ppm PPM 10.8 10.6 10.4 10.2 10.0 9.8 9.6 9.4 9.2 9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 Hd 1.216 N N Figure S5.28: 1 H NMR (500MHz) spectrum of solution of [cis-{PtCl(NH3)2}2-µ- Ha Cl qzn](ClO4)2 in D2O at 30 °C showing quinazoline ring proton assignment. Cl NH 3 Hb Pt Hc NH 3 1.200 H d Hc Pt H e Hf 1.473 N H 3 N H 3 He
- 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
- 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 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
- Page 298 and 299: List of Figures Figure 6.1: Spectro
- Page 300 and 301: Chapter 6 Tuning Reactivity of Plat
- Page 302 and 303: Against this background, several re
- Page 304 and 305: 6.2.2 Instruments Microanalyses wer
- Page 306 and 307: Metal Complex Pt3 Yield: 52.5 mg (0
- Page 308 and 309: 6.3 Results 6.3.1 Synthesis and Cha
- Page 310 and 311: The pKa values obtained are summari
- Page 312 and 313: Table 6.2: DFT-calculated parameter
- Page 314 and 315: that of dinuclear Pt(II) complexes
- Page 316 and 317: It can be concluded that substituti
- Page 318 and 319: ate constants, kobs(1 st /2 nd ), w
- Page 320 and 321: Table 6.3: Summary of rate constant
- Page 322 and 323: 6.3.6 Activation Parameters The act
- Page 324 and 325: pKa1 values become smaller. In addi
- Page 326 and 327: of steric influence is felt by the
- Page 328 and 329: 6.5 Conclusion The present study ha
- Page 330 and 331: 17 O. F. Wendt and L. I. Elding, 19
ln(k rd<br />
2(3 ) /T)<br />
-8.5<br />
-9.0<br />
-9.5<br />
-10.0<br />
-10.5<br />
-11.0<br />
TMTU<br />
DMTU<br />
TU<br />
-11.5<br />
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350<br />
1/T, K -1<br />
Figure S5.27: Plots <strong>of</strong> ln(k2/T) versus (1/T) for the third step reaction <strong>of</strong> qzn with a<br />
series <strong>of</strong> different nucleophiles at varying temperatures.<br />
66
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