Tuning Reactivity of Platinum(II) Complexes

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k st obs(1 ) , in s-1 0.10 0.08 0.06 0.04 0.02 0.00 TU DMTU TMTU 0.000 0.005 0.010 0.015 0.020 [NU]/ mol dm -3 Figure S7.17: Concentration dependence of kobs(1 st ), s -1 , for the simultaneous k obs(2 nd ) , in s -1 0.0010 0.0008 0.0006 0.0004 0.0002 0.0000 displacement of the coordinated water molecules in HexPt by thiourea nucleophiles, pH =2.0, T =298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). TU DMTU TMTU 0.000 0.005 0.010 0.015 0.020 0.025 [NU]/ mol dm-3 Figure S7.18: Concentration dependence of kobs(2 nd ), s -1, for the displacement of the ammine (NH3) ligand in HexPt by thiourea nucleophiles, pH =2.0, T = 298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). 50
Table S7.16: Average observed rate constants, kobs(1 st ), for the simultaneous displacement of aqua ligands in HexPt at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [HexPt]. 1/T, K -1 TU DMTU TMTU kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) kobs(1 st ), s -1 ln(k2/T) 0.00347 0.02701 -5.0040 0.01449 -5.6273 0.005154 -6.6608 0.00341 0.03642 -4.7227 0.02331 -5.1690 0.007896 -6.2514 0.00335 0.04851 -4.4530 0.03484 -4.7839 0.011452 -5.8966 0.00330 0.06134 -4.2349 0.05019 -4.4356 0.016240 -5.5639 0.00325 0.07809 -4.0099 0.07122 -4.1020 0.023000 -5.2322 Table S7.17: Average observed rate constants, kobs(2 nd ), for the displacement of ammine ligand in HexPt at varied temperatures in the range 15 to 35 °C while maintaining nucleophile concentration at ≈ 60x [HexPt]. 1/T, K -1 TU DMTU TMTU kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) kobs(2 nd ), s -1 ln(k2/T) 0.00347 2.528 x 10 -4 -9.6756 5.340 x 10 -5 -11.2307 1.986 x 10 -5 -12.2198 0.00341 4.294 x 10 -4 -9.1631 7.795 x 10 -5 -10.8695 3.349 x 10 -5 -11.7144 0.00335 6.919 x 10 -4 -8.7030 1.086 x 10 -4 -10.5554 5.472 x 10 -5 -11.2403 0.00330 1.010 x 10 -3 -8.3413 8.062 x 10 -5 -10.8694 0.00325 1.489 x 10 -3 -7.9699 2,248 x 10 -4 -9.8605 1.241 x 10 -4 -10.4546 51
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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
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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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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
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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 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
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