Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
Table S7.25: Average observed rate constants, kobs(2 nd ), for the displacement of ammine ligand in DecPt at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [DecPt]. 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 1.438 x 10 -4 -10.0871 3.781 x 10 -5 -11.4232 0.00341 2.164 x 10 -4 -9.6959 7.694 x 10 -5 -10.7298 6.608 x 10 -5 -10.8821 0.00335 3.174 x 10 -4 -9.3295 1.272 x 10 -4 -10.2442 0.00330 4.492 x 10 -4 -8.9990 1.956 x 10 -4 -9.8306 1.831 x 10 -4 -9.8967 0.00325 6.272 x 10 -4 -8.6815 3.063 x 10 -4 -9.3984 3.023 x 10 -4 -9.5115 ln(k 2(1 st ) /T) -4.0 -4.5 -5.0 -5.5 -6.0 -6.5 -7.0 -7.5 0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 60 TMTU TU DMTU Figure S7.28: Eyring plots forthe determination of the activation enthalpies and entropies for k2,1 st of all nucleophiles studied with DecPt complex.
ln(k nd 2(2 ) /T) -8.5 -9.0 -9.5 -10.0 -10.5 -11.0 -11.5 0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 61 TU DMTU TMTU Figure S7.29: Eyring plots forthe determination of the activation enthalpies and entropies for k2,2 nd of all nucleophiles studied with DecPt complex. Absorbance 0.155 0.150 0.145 0.140 0.135 0.130 0.125 2 4 6 8 10 12 Figure S7.30: UV-Vis spectra recorded for the DecPt complex in the pH range 2-10 at 25 °C. Inset: Plot of absorbance versus pH at 261 nm. pH
- Page 366 and 367: 7.3 Results 7.3.1 DFT Calculations
- Page 368 and 369: Structure HOMO LUMO EnPt (C2h) Prop
- Page 370 and 371: Absorbance Table 7.2: Summary of pK
- Page 372 and 373: coordination to the soft Pt(II) cen
- Page 374 and 375: observed at -2962.4 and -3024.1 ppm
- Page 376 and 377: H 3N NH 3 Pt NH 2 OH 2 n NH 3 NH 2
- Page 378 and 379: k obs2 , in s -1 -3 TU 1.2x10 DMTU
- Page 380 and 381: 7.3.4 Activation Parameters The tem
- Page 382 and 383: density is located on the metal cen
- Page 384 and 385: acetylmethionine, which reported th
- Page 386 and 387: References 1 (a) B. Rosenberg, L. V
- Page 388 and 389: 32 N. Summa, J. Maigut, R. Puchta a
- Page 390 and 391: Appendix 7 Table S7.1: Summary of s
- Page 392 and 393: k obs(2 nd ) , in s -1 0.00020 0.00
- Page 394 and 395: ln(k 2(2 nd ) /T) -8.5 -9.0 -9.5 -1
- Page 396 and 397: k obs(1 st ) , in s -1 0.06 TU DMTU
- Page 398 and 399: ln(k 2(1 st ) /T) -3.2 TU DMTU TMTU
- Page 400 and 401: Table S7.11: Summary of kobs(2 nd )
- Page 402 and 403: Table S7.13: Average observed rate
- Page 404 and 405: %T 22.0 20 18 16 14 12 10 8 6 4 2 0
- Page 406 and 407: k st obs(1 ) , in s-1 0.10 0.08 0.0
- Page 408 and 409: ln(k st 2(1 ) /T) -4.0 TU DMTU TMTU
- Page 410 and 411: Figure S7.23: Mass spectra for HexP
- Page 412 and 413: Table S21: Average observed rate co
- Page 414 and 415: Table S7.23: Summary of kobs(2 nd )
- Page 418 and 419: 90.0 80 70 60 50 40 30 20 %T 10 0 -
- Page 420 and 421: Figure S7.37: Mass spectrum for Hex
- Page 422 and 423: Chapter 8 Tuning Reactivity of plat
- Page 424 and 425: dinuclear Pt(II) complexes to relea
- Page 426 and 427: finally Pt2. The order of reactivit
- Page 428: • prolonged survival in the cell
ln(k nd<br />
2(2 ) /T)<br />
-8.5<br />
-9.0<br />
-9.5<br />
-10.0<br />
-10.5<br />
-11.0<br />
-11.5<br />
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350<br />
1/T, K -1<br />
61<br />
TU<br />
DMTU<br />
TMTU<br />
Figure S7.29: Eyring plots forthe determination <strong>of</strong> the activation enthalpies and<br />
entropies for k2,2 nd <strong>of</strong> all nucleophiles studied with DecPt complex.<br />
Absorbance<br />
0.155<br />
0.150<br />
0.145<br />
0.140<br />
0.135<br />
0.130<br />
0.125<br />
2 4 6 8 10 12<br />
Figure S7.30: UV-Vis spectra recorded for the DecPt complex in the pH range 2-10 at<br />
25 °C. Inset: Plot <strong>of</strong> absorbance versus pH at 261 nm.<br />
pH
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