Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
Table S6.10: Average observed rate constants, kobs(1 st ), at 298.15 K, for the reactions of Pt1 with a series of nucleophiles at different concentrations. [NU]/ M kobs(1 st ),s -1 TU DMTU TMTU SCN ¯ Br ¯ 0.00112 0.00367 0.00325 8.232 x 10 -4 0.00186 4.135 x 10 -5 0.00225 0.00791 0.00622 0.00145 0.00299 8.386 x 10 -5 0.00338 0.01105 0.00876 0.00204 0.00476 1.197 x 10 -4 0.00450 0.01457 0.01145 0.00286 0.00598 1.597 x 10 -4 0.00562 0.01917 0.01528 0.00371 0.00796 2.077 x 10 -4 Table S6.11: Average observed rate constants, kobs(2 nd ), at 298.15 K, for the reactions of Pt1 with a series of nucleophiles at different concentrations [NU]/ M kobs(1 st ),s -1 TU DMTU TMTU SCN ¯ 0.0112 1.0848 x 10 -4 5.2685 x 10 -5 8.1784 x 10 -5 4.7272 x 10 -5 0.0025 2.1573 x 10 -4 1.1820 x 10 -4 1.6592 x 10 -4 8.7770 x 10 -5 0.00338 3.2998 x 10 -4 1.7383 x 10 -4 2.4546 x 10 -4 1.3093 x 10 -4 0.0045 4.6576 x 10 -4 2.3680 x 10 -4 3.0170 x 10 -4 1.7552 x 10 -4 0.00562 5.8060 x 10 -4 2.8611 x 10 -4 4.0660 x 10 -4 2.1694 x 10 -4 49
Table S6.12(a): Average observed rate constants, kobs(1 st ), 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 kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) 0.00341 1.0020 x 10 -3 -6.8961 7.1300 x 10 -4 -7.0363 1.2210 x 10 - 0.00335 1.6610 x 10 -3 -6.4075 1.2167 x 10 -3 -6.6188 1.8849 x 10 - 0.00330 2.3843 x 10 -3 -6.0627 2.4334 x 10 -3 -6.2428 2.5404 x 10 - 0.00325 3.4351 x 10 -3 -5.7139 2.8330 x 10 -3 -5.9065 3.8539 x 10 - 50 3 3 3 3 -6.6984 -6.2788 -5.9993 -5.5989 Table S6.12(b): Average observed rate constants, kobs(1 st ), 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 SCN ¯ Br ¯ kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) 0.00341 7.1302 x 10 -4 -7.2363 8.5550 x 10 -5 -9.3567 0.00335 1.2167x 10 -3 -6.7188 1.4624 x 10 -4 -8.8375 0.00330 1.5558 x 10 -3 -6.4896 2.1610 x 10 -4 -8.4636 0.00325 2.4920 x 10 -3 -6.0349 3.8147 x 10 -4 -7.9117
- 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
- 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 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
Table S6.10: Average observed rate constants, kobs(1 st ), at 298.15 K, for the reactions <strong>of</strong><br />
Pt1 with a series <strong>of</strong> nucleophiles at different concentrations.<br />
[NU]/ M kobs(1 st ),s -1<br />
TU DMTU TMTU SCN ¯ Br ¯<br />
0.00112 0.00367 0.00325 8.232 x 10 -4 0.00186 4.135 x 10 -5<br />
0.00225 0.00791 0.00622 0.00145 0.00299 8.386 x 10 -5<br />
0.00338 0.01105 0.00876 0.00204 0.00476 1.197 x 10 -4<br />
0.00450 0.01457 0.01145 0.00286 0.00598 1.597 x 10 -4<br />
0.00562 0.01917 0.01528 0.00371 0.00796 2.077 x 10 -4<br />
Table S6.11: Average observed rate constants, kobs(2 nd ), at 298.15 K, for the reactions <strong>of</strong><br />
Pt1 with a series <strong>of</strong> nucleophiles at different concentrations<br />
[NU]/ M kobs(1 st ),s -1<br />
TU DMTU TMTU SCN ¯<br />
0.0112 1.0848 x 10 -4 5.2685 x 10 -5 8.1784 x 10 -5 4.7272 x 10 -5<br />
0.0025 2.1573 x 10 -4 1.1820 x 10 -4 1.6592 x 10 -4 8.7770 x 10 -5<br />
0.00338 3.2998 x 10 -4 1.7383 x 10 -4 2.4546 x 10 -4 1.3093 x 10 -4<br />
0.0045 4.6576 x 10 -4 2.3680 x 10 -4 3.0170 x 10 -4 1.7552 x 10 -4<br />
0.00562 5.8060 x 10 -4 2.8611 x 10 -4 4.0660 x 10 -4 2.1694 x 10 -4<br />
49
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