Tuning Reactivity of Platinum(II) Complexes

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ange 326-400 cm -1 (weak) for Pt–Cl and 1090-1100 cm -1 (broad, strong) for Cl–O (perchlorate counter ion) vibration stretches, respectively. The typical spectra are as shown in Figures S7.5, S7.15-S7.16, S7.21-S7.25 and S7.31-S7.35 (Appendix 7). The analysis data for the different complexes is as follows.(EnPt) Yield: 86.2 mg (36.0%). 1H NMR (550 MHz, D2O), δ /ppm: 2.87 (dd, 4H). 195Pt NMR (107 MHz, D2 O) δ/ppm: -2415.6. IR (KBr, 4000-300 cm -1 ) (cm -1 ): 3290, 3257, (N–H stretch); 1090-1100 (perchlorate counter ion); 326.47 (Pt–Cl stretch); 517.5 (Pt–N stretch). Anal. Calcd for C2H20N6Cl4O8Pt2.0.25 methanol: H, 2.56; C, 3.05; N, 10.66.; Found H, 2.89; C, 3.39; N, 11.03%. (PropPt) Yield: 20.7 mg (8.5%). 1 H NMR (500 MHz, D2O), δ /ppm: 3.32 (quintet, 4H); 1.28 (s/br, 2H). 195Pt NMR (107 MHz, D2 O) δ /ppm:-2421.7 IR (KBr, 4000-300 cm -1): 3073 (N-H stretch); 1090-1100 (Perchlorate counter ion); 341.8 (Pt–Cl stretch); 561.7 (Pt–N stretch); 2966, 2925 (C-H stretch). TOF MS/ES +. (m/z, M 2+): 318 (C3H10N3PtCl species). Anal. Calcd for C3H22N6Cl4O8Pt2: H, 2.76; C, 4.49; N, 10.48.; Found H, 2.56; C, 4.23; N, 9.98%. (ButPt) Yield: 60.0 mg (26.6%). 1H NMR (500 MHz, D2O) δ / ppm: 3.32 (quintet, 4H); 1.28 (s, 4H). 195Pt NMR (107 MHz, D2 O) δ / ppm: -2344.3. IR (KBr, 4000-300 cm -1): 3158, 3078 (N–H stretch); 1090-1100 (perchlorate counter ion); 333.7 (Pt–Cl stretch); 516.8 (Pt-N stretch); 2951, 2931, 2862.7 (C-H stretch). TOF MS/ES +. (m/z, M 2+): 308 (C2H12N3PtCl species). Anal. Calcd for C4H24N6Cl4O8Pt2: H, 2.96; C, 5.83; N, 10.30.; Found H, 2.95; C, 5.78; N, 9.96%. (HexPt) Yield: 98.4 mg (36.9%). 1H NMR (500 MHz, D2O) δ /ppm: 2.67 (t/br, 4H), 1.67 (s/br, 4H), 1.37 (s/br, 4H). 195 Pt NMR δ /ppm: -2420.2. IR (KBr, 4000-300 cm -1 ): 3283 (N-H stretch); 1090-1100 cm -1 (perchlorate counter ion); 324 (Pt-Cl stretch); 515.9 (Pt- N stretch); 2926.9, 2854.7 (C-H stretch). TOF MS/ES +. (m/z, M 2+): 322 (C3H14N3PtCl species). Anal. Calcd for C6H26N6Cl4Pt2: H, 3.34; C, 8.53; N, 9.96.; Found: H, 3.38; C, 9.00; N, 9.58%. 6
(OctPt) Yield: 65.0 mg (29.6%). 1 H NMR (500 MHz, D2O) δ /ppm: 2.65 (quintet, 4H); 1.55 (t, 4H), 1.28 (t, 4H). 195Pt NMR δ /ppm: -2320.4, -2461.82. IR (KBr, 4000-300 cm -1): 3268 (N–H stretch); 1090-1100 cm -1 (perchlorate counter ion); 333.7 (Pt–Cl stretch); 507 (Pt–N stretch); 2928, 2856 (C–H stretch). TOF MS/ES +. (m/z, M 2+): 336 (C4H16N3PtCl species). Anal. Calcd for C8H30N6Cl4Pt2: H, 3.70; C, 11.01; N, 9.64.; Found: H, 3.78; C, 11.44; N, 9.36%. (DecPt) Yield: 159.7 mg (59.8%). 1H NMR (500 MHz, D2O) δ /ppm: 2.64 (quintet, 4H); 1.66 (quintet, 4H); 1.28 (s/broad, 12H). 195 Pt NMR δ /ppm: -2413.2. IR (KBr, 4000-300 cm -1) : 3285.6, 3237.8 (N–H stretch); 1090-1100 cm -1 (perchlorate counter ion); 333.8 (Pt–Cl stretch); 516 (Pt–N stretch); 2925, 2853 (C-H stretch). TOF MS/ES +. (m/z, M 2+): 350 (C5H18N3PtCl species). Anal. Calcd for C10H32N6Cl4Pt2: H, 4.03; C, 13.34; N, 9.34.; Found: H, 3.94; C, 12.93; N, 9.07%. 7.2.2 Physical Measurements C, H, and N analyses were performed with a Carlo Erba Elemental Analyzer 1106. The infrared spectra (4000-300 cm -1 , KBr disc) were recorded on a Perkin Elmer Spectrum One-FTIR spectrophotometer. All NMR spectra were measured at ambient temperature of 30°C with a Bruker Avance 500 spectrometer equipped with a variable-temperature control unit. Chemical shift values are given in δ (ppm): 1 H relative to tetramethylsilane (δ = 0.00) and 195Pt were externally referenced to K2[PtCl6] in D2O. Mass spectrometric analyses were collected on Hewlett Packard LC-MS using electron impact (EI) ionization. Kinetic measurements of fast reactions were performed on an Applied Photophysics SX 18MV stopped-flow instrument coupled to an online data acquisition system. A Varian Cary 100 Bio spectrophotometer equipped with a thermostated cell holder was used to record UV–Vis spectra for the determination of the pKa values of the aqua complexes and for the study of the slow reactions. The temperature of both instruments was controlled to an accuracy of ± 0.1 °C. The pH and time-dependent kinetic spectra were graphically analysed using Origin 7.5 ® 38 software package. 7.2.3 Computational Details To gain insight to the experimental data obtained, computational calculation was carried out. The geometries and energies of molecular orbitals of aqua complexes EnPt, PropPt, 7
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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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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
Page 312 and 313: Table 6.2: DFT-calculated parameter
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Page 318 and 319: ate constants, kobs(1 st /2 nd ), w
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Page 322 and 323: 6.3.6 Activation Parameters The act
Page 324 and 325: pKa1 values become smaller. In addi
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Page 328 and 329: 6.5 Conclusion The present study ha
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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
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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
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Page 348 and 349: Table S6.10: 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
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Page 360 and 361: complexes, have a lower charge and
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
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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
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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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