Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
%T 22.0 20 18 16 14 12 10 8 6 4 2 0 -2.0 3230 3292 2931 2861 2022 2438 2157 4000.0 3600 3200 2800 2400 2000 1800 1600 cm-1 1400 1200 1000 800 600 400 300.0 Figure S7.15: Infra-red (KBr disc) spectrum for ButPt-Cl complex. Figure S7.16: Mass spectra for ButPt–Cl complex (m/e, M 2+ ). 48 1649 1593 1470 1346 1311 1267 1207 1083 931 734 806 700 624 514 383
Table S7.14: Summary of kobs(1 st ), values for simultaneous displacement of aqua ligands for HexPt complex with thiourea nucleophiles, pH = 2.0, T = 298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). Nucleophile kobs(1 st), in s -1 TU DMTU TMTU 0.004 0.01617 0.00831 0.00310 0.008 0.03219 0.01824 0.00666 0.01199 0.04851 0.02556 0.00985 0.016 0.06417 0.03564 0.01314 0.02 0.08038 0.4123 Table S7.15: Summary of kobs(2 nd ), values for displacement of ammine (NH3) ligand for HexPt complex with thiourea nucleophiles, pH = 2.0, T = 298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). Nucleophile kobs(2 nd ), in s -1 TU DMTU TMTU 0.00466 1.9050 x10 -4 5.3492 x 10 -5 1.1197 x 10 -5 0.00932 3.7897 x 10 -4 1.0092 x 10 -4 2.0541 x 10 -5 0.01398 5.6289 x 10 -4 1.4823 x 10 -4 3.1558 x 10 -5 0.01865 7.4919 x 10 -4 1.9733 x 10 -4 4.3904 x 10 -5 0.02331 9.3180 x 10 -4 2.4301 x 10 -4 5.3042 x 10 -5 49
- Page 354 and 355: SH N SH + Mechanism Br N + CO 3 2-
- Page 356 and 357: Figure 7.5: 195Pt NMR spectra of mi
- Page 358 and 359: linker remained coordinated to the
- Page 360 and 361: complexes, have a lower charge and
- Page 362 and 363: ange 326-400 cm -1 (weak) for Pt-Cl
- Page 364 and 365: ButPt, HexPt, OctPt and DecPt, were
- 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 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 416 and 417: Table S7.25: Average observed rate
- 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
%T<br />
22.0<br />
20<br />
18<br />
16<br />
14<br />
12<br />
10<br />
8<br />
6<br />
4<br />
2<br />
0<br />
-2.0<br />
3230<br />
3292<br />
2931<br />
2861<br />
2022<br />
2438 2157<br />
4000.0 3600 3200 2800 2400 2000 1800 1600<br />
cm-1<br />
1400 1200 1000 800 600 400 300.0<br />
Figure S7.15: Infra-red (KBr disc) spectrum for ButPt-Cl complex.<br />
Figure S7.16: Mass spectra for ButPt–Cl complex (m/e, M 2+ ).<br />
48<br />
1649<br />
1593<br />
1470<br />
1346<br />
1311<br />
1267<br />
1207<br />
1083<br />
931<br />
734<br />
806<br />
700<br />
624<br />
514<br />
383