29.07.2013
•
Views
43 (a) D. Jaganyi, A. Hofmann and R. van Eldik, 2001, Angew. Chem. Int. Ed., 40, 1680; (b) A. Hofmann, D. jaganyi, O. Q. Munro, G. Liehr, and R. van Eldik, 2003, Inorg. Chem., 42, 1688. 44 G. McGowan, S. Parsons and P.J. Sadler, 2005, Inorg. Chem., 44, 7459, and references cited therein. 45 M. A. Nazif, J-A. Bangert, I. Ott, R. Gust, R. Stoll and W. S. Sheldrick, 2009, J. Inorg. Biochem., 103, 1405. 46 Y. Chen and R. E. Shepherd, 1998, Inorg. Chim. Acta, 279, 85. 47 N. Summa,W. Schiess, R. Puchta, N. van Eikema Hommes and R. van Eldik, 2006. Inorg. Chem., 45, 2948. 48 N. Sato, Pyrazines and their benzo derivatives, in: A. J. Boulton (Ed.), Comprehensive Heterocyclic Chemistry II, Vol. 6(Ch. 6.03), Pergamon, Oxford, 1996. 49 G. Ge, J. He, H. Guo, H. Wang, D. Zou, 2009, J. Organomet. Chem., 694, 3050. 50 M. L. Tobe and J. Burgess, 1999, Inorganic Reaction Mechanisms, Addison Wesley Longman Ltd., NY, pp. 30-43, 70-112. 51 J. D. Atwood, 1997, Inorganic and Organometallic reaction mechanisms, 2nd Ed., Wiley-VCH, NY, pp.43-61. 52 R. G. Wilkins, 1991, Kinetics and Mechanism of reactions of Transition Metal complexes, 2nd Ed., VCH, Wienheim, pp. 199-201. 53 F. Basolo and R. G. Pearson, 1967, Mechanism of Inorganic reactions, 2nd Ed., Wiley, New York, pp. 80-115. 36
Appendix 5 Comparative Rates of Ligand Substitution in Diazine-bridged Dinuclear Platinum(II) Complexes in Aqueous Solution Table S5.1: Summary of the wavelengths (nm) used for monitoring the reactions between a series of aqua Pt(II) complexes with neutral S-donor nucleophiles. Complex Nucleophile Wavelength (λ, nm) pzn TU 395 DMTU 411 TMTU 411 pmn TU 325 DMTU 325 TMTU 325 pdn TU 342 DMTU 290 TMTU 339 qzn TU 392 DMTU 392 TMTU 343 pht TU 335 DMTU 298 TMTU 307 37
-
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:
Table S4.7: Average observed rate c
-
Page 196 and 197:
Table S4.8: Average observed rate c
-
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:
Table S4.14: Average observed rate
-
Page 204 and 205:
Table S4.18: Average observed rate
-
Page 206 and 207:
k obs(1 st ) , s -1 0.06 0.04 0.02
-
Page 208 and 209:
Table S4.23: Average observed rate
-
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 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 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:
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 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 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 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 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
-
Page 428:
• prolonged survival in the cell
Change language