Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
k obs2 , in s -1 -3 TU 1.2x10 DMTU TMTU 1.0x10 -3 8.0x10 -4 6.0x10 -4 4.0x10 -4 2.0x10 -4 0.0 0.000 0.005 0.010 0.015 0.020 0.025 0.030 [NU]/ mol dm -3 Figure 7.8: Concentration dependence of kobs(2 nd ), s-1, for the release of the ammine ligand in OctPt by thiourea nucleophiles at pH =2.0, T =298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). A summary of the values of second-order rate constants, k2,1 st/2,2 nd, calculated from the slopes of such plots at 25°C, for the first and second substitution steps, respectively is tabulated in Table 7.3. 22
Table 7.3: Summary of second order rate constants and activation parameters for flexible α, ω-alkanediamine-bridged platinum(II) complexes. Complex NU k2, 1 st /M -1 s -1 ΔH ≠ 2, 1 st /kJ mol -1 23 ΔS ≠ 2, 1 st /JK -1 mol -1 k2, 2 nd /10 -3 . M -1 s -1 ΔH ≠ 2, 2 nd /kJ mol - 1 ΔS ≠ 2, 2 nd /JK -1 mol - EnPt TU 47 ± 0.7 56 ± 1 -45 ± 3 241.0 ± 2.0 52 ± 2 -102 ± 6 DMTU 26 ± 1 48 ± 1 -76 ± 4 110.0 ± 1.0 54 ± 2 -102 ± 5 TMTU 6 ± 0.1 66 ± 2 -29 ± 5 8.7 ± 0.01 49 ± 1 -120 ± 4 PropPt TU 50 ± 1 45 ± 1 -78 ± 3 44.0 ± 0.3 60 ± 2 -70 ± 5 DMTU 27 ± 1 46 ± 0.1 -75 ± 0.4 19.8 ± 0.03 56 ± 1 -94 ± 5 TMTU 11 ± 0.3 47 ± 0.2 -92 ± 1 5.7 ± 0.1 48 ± 2 -123 ± 5 ButPt TU 46 ± 1 61 ± 3 -71 ± 11 41.4 ± 0.3 56 ± 1 -129 ± 4 DMTU 26 ± 1 65 ± 2 -61 ± 8 15.0 ± 0.1 52 ± 2 -144 ± 6 TMTU 7 ± 0.03 44 ± 3 -144 ± 10 8.3 ± 0.03 69 ± 2 -98 ± 6 HexPt TU 40 ± 0.1 37 ± 0.2 -109 ± 1 40.2 ± 0.1 64 ± 1 -56 ± 4 DMTU 21 ± 0.4 57 ± 1 -46 ± 3 10.6 ± 0.1 51 ± 2 -113 ± 7 TMTU 8 ± 0.1 54 ± 1 -67 ± 2 2.3 ± 0.02 66 ± 1 -70 ± 3 OctPt TU 34 ± 0.3 52 ± 1 -61 ± 3 45.7 ± 0.4 61 ± 1 -67 ± 4 DMTU 20 ± 0.2 47 ± 2 -81 ± 5 19.1 ± 0.1 54 ± 1 -99 ± 4 TMTU 7 ± 0.1 52 ± 1 -72 ± 4 2.6 ± 0.03 56 ± 4 -133 ± 13 DecPt TU 27 ± 0.2 50 ± 1 -74 ± 1 42.1 ± 0.3 53 ± 0.3 -98 ± 1 DMTU 19 ± 0.1 62 ± 1 -39 ± 7 7.0 ± 0.3 69 ± 1 -52 ± 3 TMTU 4 ± 0.3 53± 1 -73 ± 2 4.0 ± 0.04 73 ± 1 -40 ± 4 1
- 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
- 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 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 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
Table 7.3: Summary <strong>of</strong> second order rate constants and activation parameters for<br />
flexible α, ω-alkanediamine-bridged platinum(<strong>II</strong>) complexes.<br />
Complex NU k2, 1 st<br />
/M -1 s -1<br />
ΔH ≠ 2, 1 st<br />
/kJ mol -1<br />
23<br />
ΔS ≠ 2, 1 st<br />
/JK -1 mol -1<br />
k2, 2 nd<br />
/10 -3 . M -1 s -1<br />
ΔH ≠ 2, 2 nd<br />
/kJ mol -<br />
1<br />
ΔS ≠ 2, 2 nd<br />
/JK -1 mol -<br />
EnPt TU 47 ± 0.7 56 ± 1 -45 ± 3 241.0 ± 2.0 52 ± 2 -102 ± 6<br />
DMTU 26 ± 1 48 ± 1 -76 ± 4 110.0 ± 1.0 54 ± 2 -102 ± 5<br />
TMTU 6 ± 0.1 66 ± 2 -29 ± 5 8.7 ± 0.01 49 ± 1 -120 ± 4<br />
PropPt TU 50 ± 1 45 ± 1 -78 ± 3 44.0 ± 0.3 60 ± 2 -70 ± 5<br />
DMTU 27 ± 1 46 ± 0.1 -75 ± 0.4 19.8 ± 0.03 56 ± 1 -94 ± 5<br />
TMTU 11 ± 0.3 47 ± 0.2 -92 ± 1 5.7 ± 0.1 48 ± 2 -123 ± 5<br />
ButPt TU 46 ± 1 61 ± 3 -71 ± 11 41.4 ± 0.3 56 ± 1 -129 ± 4<br />
DMTU 26 ± 1 65 ± 2 -61 ± 8 15.0 ± 0.1 52 ± 2 -144 ± 6<br />
TMTU 7 ± 0.03 44 ± 3 -144 ± 10 8.3 ± 0.03 69 ± 2 -98 ± 6<br />
HexPt TU 40 ± 0.1 37 ± 0.2 -109 ± 1 40.2 ± 0.1 64 ± 1 -56 ± 4<br />
DMTU 21 ± 0.4 57 ± 1 -46 ± 3 10.6 ± 0.1 51 ± 2 -113 ± 7<br />
TMTU 8 ± 0.1 54 ± 1 -67 ± 2 2.3 ± 0.02 66 ± 1 -70 ± 3<br />
OctPt TU 34 ± 0.3 52 ± 1 -61 ± 3 45.7 ± 0.4 61 ± 1 -67 ± 4<br />
DMTU 20 ± 0.2 47 ± 2 -81 ± 5 19.1 ± 0.1 54 ± 1 -99 ± 4<br />
TMTU 7 ± 0.1 52 ± 1 -72 ± 4 2.6 ± 0.03 56 ± 4 -133 ± 13<br />
DecPt TU 27 ± 0.2 50 ± 1 -74 ± 1 42.1 ± 0.3 53 ± 0.3 -98 ± 1<br />
DMTU 19 ± 0.1 62 ± 1 -39 ± 7 7.0 ± 0.3 69 ± 1 -52 ± 3<br />
TMTU 4 ± 0.3 53± 1 -73 ± 2 4.0 ± 0.04 73 ± 1 -40 ± 4<br />
1
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