Tuning Reactivity of Platinum(II) Complexes

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Figure S7.37: Mass spectrum for HexPt-Cl complex (m/e, M 2+ ) Figure S7.34: Mass spectrum for OctPt-Cl complex (m/e, M 2+) 64

Figure S7.35: Mass spectrum for DecPt-Cl complex (m/e, M 2+ ) 65

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 198 and 199: k obs2 , s -1 2.40x10 -4 2.20x10 -4

Page 200 and 201: Table S4.13: Average observed rate



Page 206 and 207: k obs(1 st ) , s -1 0.06 0.04 0.02


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 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 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 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 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 346 and 347: -2304.16 ppm H 3N PPM -2200.0 -2220



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 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 418 and 419: 90.0 80 70 60 50 40 30 20 %T 10 0 -

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

complexes

ligand

substitution

nucleophiles

dmtu

tmtu

thiourea

reactions

constants

ligands

tuning

reactivity

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