Tuning Reactivity of Platinum(II) Complexes

More documents

Recommendations

Info

Figure S5.13: UV/Visible spectra for the titration of 0.1 mM pdn with NaOH in the pH range 2-10, T = 25° C. Inset is the titration curve at 240 nm. Table S5.14: Average observed rate constants, kobs(1 st ), at 298.15 K, for the displacement of the first aqua ligand of pdn with a series of nucleophiles at different concentrations. [NU]/ M kobs(1 st ), s -1 TU DMTU TMTU 0.02 0.00372 0.00502 0.00166 0.04 0.00848 0.01096 0.00280 0.06 0.01182 0.01590 0.00398 0.08 0.01672 0.02187 0.00511 0.1 0.02019 0.02879 0.00660 50
Table S5.15: Average observed rate constants, kobs(2 nd ), at 298.15 K, for the displacement of the second aqua ligand of pdn with a series of nucleophiles at different concentrations. [NU]/ M kobs(2 nd ), s -1 TU DMTU TMTU 0.02 2.029 x 10 -4 3.480 x 10 -4 — 0.04 3.932 x 10 -4 6.850 x 10 -4 2.7357 x 10 -4 0.06 6.084 x 10 -4 0.00103 4.3068 x 10 -4 0.08 8.625 x 10 -4 0.00139 5.1627 x 10 -4 0.1 1.089 x 10 -3 — 6.7520 x 10 -4 Table S5.16: Average observed rate constants, kobs(3 rd ), at 298.15 K, for the displacement of the bridging ligand of pdn with a series of nucleophiles at different concentrations. [NU]/ M kobs(3 rd ), s -1 TU DMTU TMTU 0.002 - 1.8915 x 10 -5 3.1750 x 10 -6 0.004 1.8865 x 10 -5 3.7780 x 10 -5 6.0497 x 10 -6 0.006 2.5761 x 10 -5 6.0950 x 10 -5 9.0890 x 10 -6 0.008 3.8720 x 10 -5 7.5260 x10 -5 1.3319 x 10 -5 0.01 4.6230 x 10 -5 9.4750 x 10 -5 1.5773 x 10 -5 51
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: Table S5.5: Average observed rate c
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: Table S5.9: Average observed rate c
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 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 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:
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:
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

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?