Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
Table S7.11: Summary of kobs(2 nd ), values for displacement of ammine (NH3) ligand for ButPt 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 k obs(1st) , in s -1 TU DMTU TMTU 0.00229 9.5494 x 10-5 3.5032 x 10-5 1.9006 x 10-5 0.00458 1.9802 x 10-4 6.7004 x 10-5 3.7380 x 10-5 0.00686 2.8605 x 10-4 1.0474 x 10-4 5.7338 x 10-5 0.00915 3.7232 x 10-4 1.3550 x 10-4 7.5472 x 10-5 0.01144 4.7298 x 10-4 1.7214 x 10-4 0.06 0.04 0.02 0.00 TMTU TU DMTU 0.000 0.002 0.004 0.006 0.008 0.010 0.012 [NU]/ mol dm -3 Figure S7.11: Concentration dependence of kobs(1 st ), s -1 , for the simultaneous displacement of the coordinated water molecules in ButPt by thiourea nucleophiles, pH =2.0, T =298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). 44
k obs(2 nd ) , in s -1 0.0005 TU DMTU TMTU 0.0004 0.0003 0.0002 0.0001 0.0000 0.000 0.002 0.004 0.006 0.008 0.010 0.012 [NU]/ mol dm -3 Figure S7.12: Concentration dependence of kobs(2 nd ), s -1, for the displacement of the ammine (NH3) ligand in ButPt by thiourea nucleophiles, pH =2.0, T = 298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). Table S7.12: Average observed rate constants, kobs(1 st ), for the simultaneous substitution of aqua ligands in ButPt at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [ButPt]. 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 0.01224 -5.0845 0.00684 -5.6659 0.00226 -6.7739 0.00341 0.02034 -4.5939 0.0105 -5.2547 0.00300 -6.5068 0.00335 0.03140 -4.1766 0.0174 -4.7666 0.00466 -6.0844 0.00330 0.05051 -3.7179 0.0286 -4.2986 0.00615 -5.8232 0.00325 0.06943 -3.4161 0.0388 -3.9969 0.00724 -5.6768 45
- Page 350 and 351: Table S6.13: Average observed rate
- Page 352 and 353: Absorbance 1.6 1.4 1.2 1.0 0.8 0.6
- 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 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 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
Table S7.11: Summary <strong>of</strong> kobs(2 nd ), values for displacement <strong>of</strong> ammine (NH3) ligand for<br />
ButPt complex with thiourea nucleophiles, pH = 2.0, T = 298 K, I = 0.1 M<br />
(NaClO4, adjusted with 0.01 M HClO4).<br />
Nucleophile kobs(2 nd ), in s -1<br />
k obs(1st) , in s -1<br />
TU DMTU TMTU<br />
0.00229 9.5494 x 10-5 3.5032 x 10-5 1.9006 x 10-5<br />
0.00458 1.9802 x 10-4 6.7004 x 10-5 3.7380 x 10-5<br />
0.00686 2.8605 x 10-4 1.0474 x 10-4 5.7338 x 10-5<br />
0.00915 3.7232 x 10-4 1.3550 x 10-4 7.5472 x 10-5<br />
0.01144 4.7298 x 10-4 1.7214 x 10-4<br />
0.06<br />
0.04<br />
0.02<br />
0.00<br />
TMTU<br />
TU<br />
DMTU<br />
0.000 0.002 0.004 0.006 0.008 0.010 0.012<br />
[NU]/ mol dm -3<br />
Figure S7.11: Concentration dependence <strong>of</strong> kobs(1 st ), s -1 , for the simultaneous<br />
displacement <strong>of</strong> the coordinated water molecules in ButPt by thiourea<br />
nucleophiles, pH =2.0, T =298 K, I = 0.1 M (NaClO4, adjusted with 0.01<br />
M HClO4).<br />
44
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