Tuning Reactivity of Platinum(II) Complexes

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ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0 -9.5 -10.0 -10.5 -11.0 -11.5 -12.0 -12.5 -13.0 -13.5 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 44 DMTU TMTU Figure S5.6: Plots of ln(k2/T) versus (1/T) for the second step reaction of pzn with a ln(k 2 /T) -13 -14 -15 -16 -17 -18 -19 series of different nucleophiles at varying temperatures. TU DMTU TMTU 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350 1/T, K -1 Figure S5.7: Plots of ln(k3/T) versus (1/T) for the third step reaction of pzn with a series of different nucleophiles at varying temperatures.
SpinWorks 2.5: C-PZN in H2O/D2O NH 3 Cl Pt NH 3 NH 3 N N Pt Cl 2+ NH 3 PPM 9.16 9.14 9.12 9.10 9.08 9.06 9.04 9.02 9.00 8.98 8.96 8.94 8.92 8.90 8.88 8.86 8.84 8.82 8.80 8.78 8.76 8.74 PPM 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 Figure S5.8: 1H NMR (500MHz) spectrum of solution of [cis-{PtCl(NH3)2}2-µ-pzn](ClO4)2 in D2O at 30 °C showing pyrazine ring proton assignment 45
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Tuning Reactivity of Platinum(II) C
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Declaration This thesis report is b
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Abstract Systematic kinetic and the
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Table of contents Acknowledgements
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2.5.5 Effect of Non-participating G
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5.2.1 Chemical and Solutions ......
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7.2 Experimental Section ..........
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procurements, Messers P. Forder and
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Figure 2.2 Potential energy profile
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Figure 4.6 Concentration dependence
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Figure 6.1 Spectrophotometric titra
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List of Tables Table 2.1 A selectio
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Table 6.4 Summary of rate constants
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TU thiourea DMTU 1,3-dimethyl-2-thi
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Table of Contents-1 Chapter 1 .....
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1.0 Introduction 1.1 Cancer Disease
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toxic potential. The most well-know
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1.3.2.2 Cellular Uptake Cisplatin i
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H 3N OH 2 Pt H 3N OH 2 Active Pt(II
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transformational pathways that comp
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the hydrolysis of the complex, wher
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1.3.4 Terpyridine Platinum(II) Comp
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H 3 N Cl Pt NH 3 H 3 N NH 2 (CH 2 )
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1.4 Kinetic Interest The platinum-b
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3. The effect of varying the positi
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17 R. A. Henderson, The Mechanism o
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Altona J. H. van Boom, G. A. van de
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76 (a)J. Kašpárková, J. Zehnulov
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Table of Contents-2 Chapter Two ...
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List of Tables Table 2.1: A selecti
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The mononuclear Pt(II) complexes 1-
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Potential Energy R + X RX 1 transit
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For the associative mechanism (A),
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the concentration of one of the rea
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k obs , s -1 0.00030 0.00025 0.0002
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k = Ae -Ea/RT 2.14 lnk = lnA - E a
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= 23.76 + R Hence, a plot of ln ⎛
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iii. # Δ V ≈ 10 cm3 mol-1 featur
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conventional methods are classical
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Figure 2.6: Schematic diagram of a
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The light transmitted from the samp
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c. Oxidizability: Ligands that are
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Table 2.1: A selection of n o pt va
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eaction with different nucleophiles
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eaction site from direct attack by
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PEt 3 PEt 3 R PEt 3 Pt Pt Y Y Cl R
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direct displacement of the leaving
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therefore, weaken the bond of the l
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σ-Donation According to classical
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References 1 (a) J. Reedijk, Chem.
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34 R. B. Jordan, Reaction Mechanism
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Table of Contents-3 Chapter 3.The
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Chapter 3 The π-Acceptor Effect in
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In order to extend our understandin
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after which water was added to quen
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O CH 3 + I + N O oH - N O O 7 CH 3
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84% (34.7 mg, 0.0618 mmol). 1 H NMR
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PhCN PhCN Pt Cl Cl + N N CH 3 N CH
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Complex Structure HOMO LUMO PtCl CH
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The geometry-optimised structures i
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against the concentration of the in
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Table 3.2: Summary of the second-or
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constants of CH3PhisoqPtCl decrease
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with π*-orbitals of the ligand. Th
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3.6 References 1 D. Rosenberg, L. V
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30 Microcal TM Origin TM Version 5.
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Figure S3.1: Kinetic trace at 448 n
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ln(k 2 /T) -6.0 -7.5 -9.0 -10.5 -12
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Table S3.3b: Average observed rate
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Table S3.5b: Temperature dependence
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Table S3.8: DFT calculated electros
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List of Figures Figure 4.1: Structu
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Table 4.2: Summary of pKa values fo
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4.1 Introduction Platinum compounds
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cis geometry, leading to dramatic c
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ligand was added to the [{cis-PtCl(
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spectra were measured in and refere
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4.3.1 DFT calculated Optimized Stru
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Table 4.1: A summary of the DFT cal
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H2O-Pt-L-Pt-OH2 H2O-Pt-L-Pt-OH2 H2O
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electrophilicity and acidity of the
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(A) 18 Absorbance 0.08 0.07 0.06 0.
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k obs(3 rd ) , s -1 -5 6.00x10 TMTU
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4.3.4 Kinetics with NMR The substit
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ln([ML] t ) 4.0 3.5 3.0 2.5 2.0 1.5
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ln(k 2(1 st ) /T) -3.5 -4.0 -4.5 -5
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Comple x Table 4.4: Summary of Acti
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The decrease in reactivity of 2,6pz
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Table 4.5: DFT calculated (NBO) cha
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eaction proceeds via bimolecular pa
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References 1 T. Storr, K. H.Thomson
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36 D. Jaganyi, D. Reddy, J.A. Gerte
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Appendix 4 THE INFLUENCE OF THE PYR
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Absorbance at 368. 0 nm 0. 0 8 0. 0
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Table S4.3: Average observed rate c
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k nd obs(2 ) , s-1 0.003 TU DMTU TM
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k obs2 , s -1 2.40x10 -4 2.20x10 -4
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Table S4.13: Average observed rate
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k obs(1 st ) , s -1 0.06 0.04 0.02
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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 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 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
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The pKa values obtained are summari
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Table 6.2: DFT-calculated parameter
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that of dinuclear Pt(II) complexes
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It can be concluded that substituti
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ate constants, kobs(1 st /2 nd ), w
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Table 6.3: Summary of rate constant
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6.3.6 Activation Parameters The act
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pKa1 values become smaller. In addi
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of steric influence is felt by the
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6.5 Conclusion The present study ha
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17 O. F. Wendt and L. I. Elding, 19
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51 Y. Iwadata, K. Kawamura, K. Igar
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Table S6.4(b): Average observed rat
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ln(k 2(2 nd ) /T) -4 -6 -8 -10 -12
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45.0 40 35 30 25 20 %T 15 10 5 0 -5
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k st obs(1 ) in s-1 0.30 Br TU 0.25
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-2304.16 ppm H 3N PPM -2200.0 -2220
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Absorbance 1.6 1.4 1.2 1.0 0.8 0.6
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SH N SH + Mechanism Br N + CO 3 2-
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Figure 7.5: 195Pt NMR spectra of mi
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linker remained coordinated to the
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complexes, have a lower charge and
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ange 326-400 cm -1 (weak) for Pt-Cl
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ButPt, HexPt, OctPt and DecPt, were
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7.3 Results 7.3.1 DFT Calculations
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Structure HOMO LUMO EnPt (C2h) Prop
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Absorbance Table 7.2: Summary of pK
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coordination to the soft Pt(II) cen
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observed at -2962.4 and -3024.1 ppm
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H 3N NH 3 Pt NH 2 OH 2 n NH 3 NH 2
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k obs2 , in s -1 -3 TU 1.2x10 DMTU
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7.3.4 Activation Parameters The tem
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density is located on the metal cen
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acetylmethionine, which reported th
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References 1 (a) B. Rosenberg, L. V
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32 N. Summa, J. Maigut, R. Puchta a
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Appendix 7 Table S7.1: Summary of s
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k obs(2 nd ) , in s -1 0.00020 0.00
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ln(k 2(2 nd ) /T) -8.5 -9.0 -9.5 -1
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k obs(1 st ) , in s -1 0.06 TU DMTU
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ln(k 2(1 st ) /T) -3.2 TU DMTU TMTU
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Table S7.11: Summary of kobs(2 nd )
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%T 22.0 20 18 16 14 12 10 8 6 4 2 0
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k st obs(1 ) , in s-1 0.10 0.08 0.0
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ln(k st 2(1 ) /T) -4.0 TU DMTU TMTU
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Figure S7.23: Mass spectra for HexP
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Table S21: Average observed rate co
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Table S7.23: Summary of kobs(2 nd )
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90.0 80 70 60 50 40 30 20 %T 10 0 -
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Figure S7.37: Mass spectrum for Hex
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Chapter 8 Tuning Reactivity of plat
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dinuclear Pt(II) complexes to relea
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finally Pt2. The order of reactivit
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• prolonged survival in the cell
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Tuning Reactivity of Platinum(II) Complexes

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