Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
Table S6.13: Average observed rate constants, kobs(2 nd ), for the reactions of Pt1 at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [Pt1]. 1/T, K -1 TU DMTU TMTU SCN - kobs(2 nd ), 10 -4 s -1 ln(k2/T) kobs(2 nd ), 10 -4 s -1 ln(k2/T) kobs(2 nd ), 51 10 -4 s -1 ln(k2/T) kobs(2 nd ), 10 -4 s -1 ln(k2/T) 0.00347 0.7128 -9.5220 0.3344 -10.279 0.2856 -10.4365 0.3363 -10.2731 0.00341 0.9226 -9.2812 0.4899 -9.9142 0.4248 -10.0568 0.5048 -9.8843 0.00335 1.312 -8.9457 0.6688 -9.6198 0.6143 -9.7049 0.8724 -9.3541 0.00330 1.958 -8.5623 1.0243 -9.2102 0.8726 -9.3705 1.2835 -8.9846 0.00325 2.736 -8.2439 1.4646 -8.869 1.1887 -9.0777 1.9770 -8.5690 0.00319 — — — — 1.5081 -8.8558 — — Figure S6.18: 1H NMR spectrum of Pt1–Cl in DMF-d7 at 30 °C
Figure S6.19: 195 Pt NMR spectrum of Pt2–Cl in DMF-d7 at 30 °C 55 50 45 40 35 %T 30 25 20 15 10 5 0.0 3786 3702 3318 3090 2378 1810 1741 4000.0 3600 3200 2800 2400 2000 1800 1600 cm-1 1400 1200 1000 800 600 400 250.0 Figure S6.20: Infra red (IR, KBr disc) spectrum of Pt2–Cl. 52 1601 1420 1330 1213 1092 838 624 547 592
- 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
- Page 332 and 333: 51 Y. Iwadata, K. Kawamura, K. Igar
- Page 334 and 335: Table S6.3: Average observed rate c
- Page 336 and 337: Table S6.4(b): Average observed rat
- Page 338 and 339: ln(k 2(2 nd ) /T) -4 -6 -8 -10 -12
- Page 340 and 341: 45.0 40 35 30 25 20 %T 15 10 5 0 -5
- Page 342 and 343: k st obs(1 ) in s-1 0.30 Br TU 0.25
- Page 344 and 345: Table S6.9: Average observed rate c
- Page 346 and 347: -2304.16 ppm H 3N PPM -2200.0 -2220
- Page 348 and 349: Table S6.10: 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
Table S6.13: Average observed rate constants, kobs(2 nd ), for the reactions <strong>of</strong> Pt1 at varied<br />
temperatures in the range 15 to 35 °C while maintaining nucleophile<br />
concentration at ≈ 60x [Pt1].<br />
1/T, K -1 TU DMTU TMTU SCN -<br />
kobs(2 nd ),<br />
10 -4 s -1<br />
ln(k2/T) kobs(2 nd ),<br />
10 -4 s -1<br />
ln(k2/T) kobs(2 nd ),<br />
51<br />
10 -4 s -1<br />
ln(k2/T) kobs(2 nd ),<br />
10 -4 s -1<br />
ln(k2/T)<br />
0.00347 0.7128 -9.5220 0.3344 -10.279 0.2856 -10.4365 0.3363 -10.2731<br />
0.00341 0.9226 -9.2812 0.4899 -9.9142 0.4248 -10.0568 0.5048 -9.8843<br />
0.00335 1.312 -8.9457 0.6688 -9.6198 0.6143 -9.7049 0.8724 -9.3541<br />
0.00330 1.958 -8.5623 1.0243 -9.2102 0.8726 -9.3705 1.2835 -8.9846<br />
0.00325 2.736 -8.2439 1.4646 -8.869 1.1887 -9.0777 1.9770 -8.5690<br />
0.00319 — — — — 1.5081 -8.8558 — —<br />
Figure S6.18: 1H NMR spectrum <strong>of</strong> Pt1–Cl in DMF-d7 at 30 °C
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