Tuning Reactivity of Platinum(II) Complexes

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Table 4.4. Summary of Activation parameters for the substitution of coordinated water ligands and the displacement of the linker by thiourea nucleophiles in [cis-{PtOH2(NH3)2-μ-pzn] +4 complexes ……………………………………………………………………………………………..28 Table 4.5. DFT calculated (NBO) charges for Pt atoms of optimised structures of monoaquaTU-substituted complexes ………………….32 Table 5.1. A summary of DFT-calculated parameters for the aqua complexes pzn to pht. The table is ordered according to increasing values of Natural Atomic charges (NBO) of Pt(II) centres ………………………10 Table 5.2 Acid dissociation constants of platinum(II) complexes determined spectrophotometrically at 25 °C (Ionic strength, I = 0.1 M NaClO4/ HClO4) …………………………………………………………………………………...14 Table 5.3. A summary of DFT calculated Parameters for aqua/hydroxo complex systems of benzodiazines and their monocyclic analogues ………………………………………………………………………………16 Table 5.4 Summary of second order rate constants of diazine-bridged dinuclear Pt(II) complexes; I = 0.1 M (NaClO4, adjusted with HClO4), T = 298.15 K ………………………………………………………………23 Table 5.5 Summary of Activation parameters for the displacement of coordinated water by a series of nucleophiles in complexes of the Type [cis-{PtOH2(NH3)2-μ-pzn] +4 , I = 0.1 M NaClO4 …….….…………27 Table 6.1 Summary of the pKa values obtained for the deprotonation of platinum-bound water of the different complexes …………………...11 Table 6.2 DFT-calculated parameters for platinum(II)complexes ……………13 Table 6.3 Summary of rate constants and activation parameters with the corresponding standard deviations for the substitution of aqua ligands by neutral (TU, DMTU, and TMTU) and ionic (I¯, Br¯ and SCN¯) nucleophiles, I = 0.10 M (NaClO4) …………………………………..21 xviii
Table 6.4 Summary of rate constants and activation parameters with the corresponding standard deviations for the replacement of bridging ligand by neutral (TU, DMTU, and TMTU) and ionic (I¯, Br¯ and SCN¯) nucleophiles, I = 0.10 M (NaClO4) …………….………...22 Table 7.1 Summary of selected DFT-calculated NBO charges, HOMO-LUMO energy gaps, Bond lengths and angles of the studied Pt(II) complexes ……………………………………………………………………………..11 Table 7.2 Summary of pKa values for the deprotonation steps of aqua platinum(II) complexes at 25 °C………………………………………………14 Table 7.3 Summary of second-order rate constants and activation parameters for flexible α,ω-alkanediamine-bridged platinum(II) complexes………………………………………………………………………………23 xix
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: List of Tables Table 2.1 A selectio
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
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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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Page 196 and 197:
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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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ln(k 2(3 rd ) /T) -10.0 -10.5 -11.0
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SpinWorks 2.5: 2,6 pznClO4 in D2O N
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Table of Contents-5 Chapter 5 .....
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List of Tables Table 5.1: A summary
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5.1 Introduction Multinuclear plati
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onding. For this reason, pKa titrat
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400-300 cm -1): 3308, 3117, 3071 (N
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5.2.6 Spectrophotometric pKa Titrat
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Table 5.1: A summary of DFT-calcula
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However, because the highest occupi
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Table 5.2: Acid dissociation consta
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Table 5.3: A summary of DFT calcula
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H3N 6 eq TU 0 eq TU Ha NH3 Ha Cl TU
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third step due to the trans-effect
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[H 2 O-Pt-(NN)-Pt-OH 2 ] +4 [NU-Pt-
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k obs(1st) / s -1 0.20 TU DMTU TMTU
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thiourea nucleophile is large enoug
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ln(k st 2(1 ) /T) -3 -4 -5 -6 -7 -8
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is the same as the electron-withdra
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associative mode of substitution me
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16 H. Ertürk, J. Maigut, R. Puchta
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43 (a) D. Jaganyi, A. Hofmann and R
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276 nm Absorbance 0 . 6 5 0 . 6 4 0
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k obs(1 st ) , s -1 0.4 0.3 0.2 0.1
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ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0
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pzn PPM -1750.0 -1850.0 -1950.0 -20
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Figure S5.13: UV/Visible spectra fo
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k obs(1 st ) in s -1 0.030 0.025 0.
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ln(k 2(2 nd ) /T) -10 -11 -12 -13 -
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9.61 ppm Ha PPM 9.8 9.6 9.4 9.2 9.0
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k obs(3rd) / s -1 -5 8 .00 x 10 T U
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ln(k st 2(1 ) /T) -1.5 TU DMTU TMTU
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ln(k rd 2(3 ) /T) -8.5 -9.0 -9.5 -1
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SpinWorks 2.5: znPt(II)-OP4 in D2O
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Figure S5.31: Mass spectrum for com
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ln(k st 2(1 ) /T) -4 -5 -6 -7 -8 -9
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SpinWorks 2.5: phtPt(II)-OP2 in D2O
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Figure S5.41: Mass spectrum for com
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List of Figures Figure 6.1: Spectro
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Chapter 6 Tuning Reactivity of Plat
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Against this background, several re
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6.2.2 Instruments Microanalyses wer
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Metal Complex Pt3 Yield: 52.5 mg (0
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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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