Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
ate constants, kobs(1 st /2 nd ), were plotted against nucleophile concentration. A linear dependency of the observed rate constants on the concentration of the nucleophiles was obtained as shown for Pt1 complex in Figures 6.5 and 6.6 (also Figures S6.1-S6.2 and S6.9-S6.10, Appendix 6). The second-order rate constants, k2(1 st /2 nd), were derived from the slopes of the plots and are summarized for all the complexes investigated in this study in Tables 3 and 4. k obs(1st) , s -1 0.020 0.016 0.012 0.008 0.004 0.000 TU DMTU TMTU SCN Br 0.000 0.001 0.002 0.003 0.004 0.005 0.006 [NU]/ mol dm -3 Figure 6.5: Concentration dependence of kobs(1 st ) for the simultaneous substitution of aqua ligands in Pt1 by thiourea nucleophiles and ionic nucleophiles at pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). 19
k obs(2nd) , s -1 0.0006 SCN TU DMTU TMTU 0.0004 0.0002 0.0000 0.000 0.001 0.002 0.003 0.004 0.005 0.006 [NU]/ mol dm -3 Figure 6.6: Concentration dependence of kobs(2 nd ) for the dissociation of bridging ligand in Pt1 by thiourea nucleophiles and ionic nucleophiles at pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4). 20
- Page 268 and 269: k obs(1 st ) in s -1 0.030 0.025 0.
- Page 270 and 271: Table S5.17: Average observed rate
- Page 272 and 273: ln(k 2(2 nd ) /T) -10 -11 -12 -13 -
- Page 274 and 275: 9.61 ppm Ha PPM 9.8 9.6 9.4 9.2 9.0
- Page 276 and 277: Table S5.22: Average observed rate
- Page 278 and 279: k obs(3rd) / s -1 -5 8 .00 x 10 T U
- Page 280 and 281: ln(k st 2(1 ) /T) -1.5 TU DMTU TMTU
- Page 282 and 283: ln(k rd 2(3 ) /T) -8.5 -9.0 -9.5 -1
- Page 284 and 285: SpinWorks 2.5: znPt(II)-OP4 in D2O
- Page 286 and 287: Figure S5.31: Mass spectrum for com
- Page 288 and 289: Table S5.28: Average observed rate
- Page 290 and 291: Table S5.29: Average observed rate
- Page 292 and 293: ln(k st 2(1 ) /T) -4 -5 -6 -7 -8 -9
- Page 294 and 295: SpinWorks 2.5: phtPt(II)-OP2 in D2O
- Page 296 and 297: Figure S5.41: Mass spectrum for com
- 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 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 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
k obs(2nd) , s -1<br />
0.0006 SCN<br />
TU<br />
DMTU<br />
TMTU<br />
0.0004<br />
0.0002<br />
0.0000<br />
0.000 0.001 0.002 0.003 0.004 0.005 0.006<br />
[NU]/ mol dm -3<br />
Figure 6.6: Concentration dependence <strong>of</strong> kobs(2 nd ) for the dissociation <strong>of</strong> bridging ligand<br />
in Pt1 by thiourea nucleophiles and ionic nucleophiles at pH = 2.0, T =<br />
298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4).<br />
20
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