Tuning Reactivity of Platinum(II) Complexes

More documents

Recommendations

Info

Table S21: Average observed rate constants, kobs(2 nd ), for the displacement of ammine ligand in OctPt at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [OctPt]. 1/T, K -1 TU DMTU TMTU kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) 0.00347 2.934 x 10 -4 -9.6692 1.161 x 10 -4 -10.5960 0.00341 4.795 x 10 -4 -9.1952 1.791 x 10 -4 -10.1799 2.439 x 10 -5 -12.1740 0.00335 7.229 x 10 -4 -8.80171 2.758 x 10 -4 -9.7652 4.855 x 10 -5 -11.5023 0.00330 1.111 x 10 -3 -8.3885 3.648 x 10 -4 -9.5021 1.021 x 10 -4 -10.7756 0.00325 1.572 x 10 -3 -8.0575 5.251 x 10 -4 -9.1543 2.037 x 10 -4 -10.1013 35.0 34 32 30 28 26 24 22 20 18 %T 16 14 12 10 8 6 4 2 0.0 (KBr disc) 3307 3233 2929 2855 2637 2149 2005 1648 1590 3600.0 3200 2800 2400 2000 1800 1600 cm-1 1400 1200 1000 800 600 330.0 1464 56 1351 1312 1299 Figure S7.24: Infrared (KBr disc) spectrum for OctPt complex 1240 1075 854 733 931 807 623 408 464 391 513
Figure S7.25: Mass spectra for OctPt–Cl complex (m/e, M 2+) Table S7.22: Summary of kobs(1 st ), values for simultaneous displacement of aqua ligands for DecPt complex with thiourea nucleophiles, pH = 2.0, T = 298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). Nucleophile kobs(1 st ), in s -1 TU DMTU TMTU 0.004 0.01067 0.00764 0.00247 0.008 0.02211 0.01507 0.00372 0.012 0.03325 0.02204 0.00490 0.016 0.04260 0.02986 0.02 0.05325 0.03798 0.00671 57
Page 1 and 2:
Tuning Reactivity of Platinum(II) C
Page 3 and 4:
Declaration This thesis report is b
Page 5 and 6:
Abstract Systematic kinetic and the
Page 7 and 8:
Table of contents Acknowledgements
Page 9 and 10:
2.5.5 Effect of Non-participating G
Page 11 and 12:
5.2.1 Chemical and Solutions ......
Page 13 and 14:
7.2 Experimental Section ..........
Page 15 and 16:
procurements, Messers P. Forder and
Page 17 and 18:
Figure 2.2 Potential energy profile
Page 19 and 20:
Figure 4.6 Concentration dependence
Page 21 and 22:
Figure 6.1 Spectrophotometric titra
Page 23 and 24:
List of Tables Table 2.1 A selectio
Page 25 and 26:
Table 6.4 Summary of rate constants
Page 27 and 28:
TU thiourea DMTU 1,3-dimethyl-2-thi
Page 30 and 31:
Table of Contents-1 Chapter 1 .....
Page 32 and 33:
1.0 Introduction 1.1 Cancer Disease
Page 34 and 35:
toxic potential. The most well-know
Page 36 and 37:
1.3.2.2 Cellular Uptake Cisplatin i
Page 38 and 39:
H 3N OH 2 Pt H 3N OH 2 Active Pt(II
Page 40 and 41:
transformational pathways that comp
Page 42 and 43:
the hydrolysis of the complex, wher
Page 44 and 45:
1.3.4 Terpyridine Platinum(II) Comp
Page 46 and 47:
H 3 N Cl Pt NH 3 H 3 N NH 2 (CH 2 )
Page 48 and 49:
1.4 Kinetic Interest The platinum-b
Page 50 and 51:
3. The effect of varying the positi
Page 52 and 53:
17 R. A. Henderson, The Mechanism o
Page 54 and 55:
Altona J. H. van Boom, G. A. van de
Page 56 and 57:
76 (a)J. Kašpárková, J. Zehnulov
Page 58 and 59:
Table of Contents-2 Chapter Two ...
Page 60 and 61:
List of Tables Table 2.1: A selecti
Page 62 and 63:
The mononuclear Pt(II) complexes 1-
Page 64 and 65:
Potential Energy R + X RX 1 transit
Page 66 and 67:
For the associative mechanism (A),
Page 68 and 69:
the concentration of one of the rea
Page 70 and 71:
k obs , s -1 0.00030 0.00025 0.0002
Page 72 and 73:
k = Ae -Ea/RT 2.14 lnk = lnA - E a
Page 74 and 75:
= 23.76 + R Hence, a plot of ln ⎛
Page 76 and 77:
iii. # Δ V ≈ 10 cm3 mol-1 featur
Page 78 and 79:
conventional methods are classical
Page 80 and 81:
Figure 2.6: Schematic diagram of a
Page 82 and 83:
The light transmitted from the samp
Page 84 and 85:
c. Oxidizability: Ligands that are
Page 86 and 87:
Table 2.1: A selection of n o pt va
Page 88 and 89:
eaction with different nucleophiles
Page 90 and 91:
eaction site from direct attack by
Page 92 and 93:
PEt 3 PEt 3 R PEt 3 Pt Pt Y Y Cl R
Page 94 and 95:
direct displacement of the leaving
Page 96 and 97:
therefore, weaken the bond of the l
Page 98 and 99:
σ-Donation According to classical
Page 100 and 101:
References 1 (a) J. Reedijk, Chem.
Page 102 and 103:
34 R. B. Jordan, Reaction Mechanism
Page 104 and 105:
Table of Contents-3 Chapter 3.The
Page 106 and 107:
Chapter 3 The π-Acceptor Effect in
Page 108 and 109:
In order to extend our understandin
Page 110 and 111:
after which water was added to quen
Page 112 and 113:
O CH 3 + I + N O oH - N O O 7 CH 3
Page 114 and 115:
84% (34.7 mg, 0.0618 mmol). 1 H NMR
Page 116 and 117:
PhCN PhCN Pt Cl Cl + N N CH 3 N CH
Page 118 and 119:
Complex Structure HOMO LUMO PtCl CH
Page 120 and 121:
The geometry-optimised structures i
Page 122 and 123:
against the concentration of the in
Page 124 and 125:
Table 3.2: Summary of the second-or
Page 126 and 127:
constants of CH3PhisoqPtCl decrease
Page 128 and 129:
with π*-orbitals of the ligand. Th
Page 130 and 131:
3.6 References 1 D. Rosenberg, L. V
Page 132 and 133:
30 Microcal TM Origin TM Version 5.
Page 134 and 135:
Figure S3.1: Kinetic trace at 448 n
Page 136 and 137:
ln(k 2 /T) -6.0 -7.5 -9.0 -10.5 -12
Page 138 and 139:
Table S3.3b: Average observed rate
Page 140 and 141:
Table S3.5b: Temperature dependence
Page 142 and 143:
Table S3.8: DFT calculated electros
Page 144 and 145:
List of Figures Figure 4.1: Structu
Page 146 and 147:
Table 4.2: Summary of pKa values fo
Page 148 and 149:
4.1 Introduction Platinum compounds
Page 150 and 151:
cis geometry, leading to dramatic c
Page 152 and 153:
ligand was added to the [{cis-PtCl(
Page 154 and 155:
spectra were measured in and refere
Page 156 and 157:
4.3.1 DFT calculated Optimized Stru
Page 158 and 159:
Table 4.1: A summary of the DFT cal
Page 160 and 161:
H2O-Pt-L-Pt-OH2 H2O-Pt-L-Pt-OH2 H2O
Page 162 and 163:
electrophilicity and acidity of the
Page 164 and 165:
(A) 18 Absorbance 0.08 0.07 0.06 0.
Page 166 and 167:
k obs(3 rd ) , s -1 -5 6.00x10 TMTU
Page 168 and 169:
4.3.4 Kinetics with NMR The substit
Page 170 and 171:
ln([ML] t ) 4.0 3.5 3.0 2.5 2.0 1.5
Page 172 and 173:
ln(k 2(1 st ) /T) -3.5 -4.0 -4.5 -5
Page 174 and 175:
Comple x Table 4.4: Summary of Acti
Page 176 and 177:
The decrease in reactivity of 2,6pz
Page 178 and 179:
Table 4.5: DFT calculated (NBO) cha
Page 180 and 181:
eaction proceeds via bimolecular pa
Page 182 and 183:
References 1 T. Storr, K. H.Thomson
Page 184 and 185:
36 D. Jaganyi, D. Reddy, J.A. Gerte
Page 186 and 187:
Appendix 4 THE INFLUENCE OF THE PYR
Page 188 and 189:
Absorbance at 368. 0 nm 0. 0 8 0. 0
Page 190 and 191:
Table S4.3: Average observed rate c
Page 192 and 193:
k nd obs(2 ) , s-1 0.003 TU DMTU TM
Page 194 and 195:
Page 196 and 197:
Page 198 and 199:
k obs2 , s -1 2.40x10 -4 2.20x10 -4
Page 200 and 201:
Table S4.13: Average observed rate
Page 202 and 203:
Page 204 and 205:
Page 206 and 207:
k obs(1 st ) , s -1 0.06 0.04 0.02
Page 208 and 209:
Page 210 and 211:
ln(k 2(3 rd ) /T) -10.0 -10.5 -11.0
Page 212 and 213:
SpinWorks 2.5: 2,6 pznClO4 in D2O N
Page 214 and 215:
Table of Contents-5 Chapter 5 .....
Page 216 and 217:
List of Tables Table 5.1: A summary
Page 218 and 219:
5.1 Introduction Multinuclear plati
Page 220 and 221:
onding. For this reason, pKa titrat
Page 222 and 223:
400-300 cm -1): 3308, 3117, 3071 (N
Page 224 and 225:
5.2.6 Spectrophotometric pKa Titrat
Page 226 and 227:
Table 5.1: A summary of DFT-calcula
Page 228 and 229:
However, because the highest occupi
Page 230 and 231:
Table 5.2: Acid dissociation consta
Page 232 and 233:
Table 5.3: A summary of DFT calcula
Page 234 and 235:
H3N 6 eq TU 0 eq TU Ha NH3 Ha Cl TU
Page 236 and 237:
third step due to the trans-effect
Page 238 and 239:
[H 2 O-Pt-(NN)-Pt-OH 2 ] +4 [NU-Pt-
Page 240 and 241:
k obs(1st) / s -1 0.20 TU DMTU TMTU
Page 242 and 243:
thiourea nucleophile is large enoug
Page 244 and 245:
ln(k st 2(1 ) /T) -3 -4 -5 -6 -7 -8
Page 246 and 247:
is the same as the electron-withdra
Page 248 and 249:
associative mode of substitution me
Page 250 and 251:
16 H. Ertürk, J. Maigut, R. Puchta
Page 252 and 253:
43 (a) D. Jaganyi, A. Hofmann and R
Page 254 and 255:
276 nm Absorbance 0 . 6 5 0 . 6 4 0
Page 256 and 257:
k obs(1 st ) , s -1 0.4 0.3 0.2 0.1
Page 258 and 259:
Page 260 and 261:
ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0
Page 262 and 263:
pzn PPM -1750.0 -1850.0 -1950.0 -20
Page 264 and 265:
Page 266 and 267:
Figure S5.13: UV/Visible spectra fo
Page 268 and 269:
k obs(1 st ) in s -1 0.030 0.025 0.
Page 270 and 271:
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:
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:
Page 290 and 291:
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 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:
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:
Page 346 and 347:
-2304.16 ppm H 3N PPM -2200.0 -2220
Page 348 and 349:
Page 350 and 351:
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 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 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
show all

Tuning Reactivity of Platinum(II) Complexes

Create successful ePaper yourself

Delete template?

Save as template?