Tuning Reactivity of Platinum(II) Complexes

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k obs2 , in s -1 -3 TU 1.2x10 DMTU TMTU 1.0x10 -3 8.0x10 -4 6.0x10 -4 4.0x10 -4 2.0x10 -4 0.0 0.000 0.005 0.010 0.015 0.020 0.025 0.030 [NU]/ mol dm -3 Figure 7.8: Concentration dependence of kobs(2 nd ), s-1, for the release of the ammine ligand in OctPt by thiourea nucleophiles at pH =2.0, T =298 K, I = 0.1 M (NaClO4, adjusted with 0.01 M HClO4). A summary of the values of second-order rate constants, k2,1 st/2,2 nd, calculated from the slopes of such plots at 25°C, for the first and second substitution steps, respectively is tabulated in Table 7.3. 22
Table 7.3: Summary of second order rate constants and activation parameters for flexible α, ω-alkanediamine-bridged platinum(II) complexes. Complex NU k2, 1 st /M -1 s -1 ΔH ≠ 2, 1 st /kJ mol -1 23 ΔS ≠ 2, 1 st /JK -1 mol -1 k2, 2 nd /10 -3 . M -1 s -1 ΔH ≠ 2, 2 nd /kJ mol - 1 ΔS ≠ 2, 2 nd /JK -1 mol - EnPt TU 47 ± 0.7 56 ± 1 -45 ± 3 241.0 ± 2.0 52 ± 2 -102 ± 6 DMTU 26 ± 1 48 ± 1 -76 ± 4 110.0 ± 1.0 54 ± 2 -102 ± 5 TMTU 6 ± 0.1 66 ± 2 -29 ± 5 8.7 ± 0.01 49 ± 1 -120 ± 4 PropPt TU 50 ± 1 45 ± 1 -78 ± 3 44.0 ± 0.3 60 ± 2 -70 ± 5 DMTU 27 ± 1 46 ± 0.1 -75 ± 0.4 19.8 ± 0.03 56 ± 1 -94 ± 5 TMTU 11 ± 0.3 47 ± 0.2 -92 ± 1 5.7 ± 0.1 48 ± 2 -123 ± 5 ButPt TU 46 ± 1 61 ± 3 -71 ± 11 41.4 ± 0.3 56 ± 1 -129 ± 4 DMTU 26 ± 1 65 ± 2 -61 ± 8 15.0 ± 0.1 52 ± 2 -144 ± 6 TMTU 7 ± 0.03 44 ± 3 -144 ± 10 8.3 ± 0.03 69 ± 2 -98 ± 6 HexPt TU 40 ± 0.1 37 ± 0.2 -109 ± 1 40.2 ± 0.1 64 ± 1 -56 ± 4 DMTU 21 ± 0.4 57 ± 1 -46 ± 3 10.6 ± 0.1 51 ± 2 -113 ± 7 TMTU 8 ± 0.1 54 ± 1 -67 ± 2 2.3 ± 0.02 66 ± 1 -70 ± 3 OctPt TU 34 ± 0.3 52 ± 1 -61 ± 3 45.7 ± 0.4 61 ± 1 -67 ± 4 DMTU 20 ± 0.2 47 ± 2 -81 ± 5 19.1 ± 0.1 54 ± 1 -99 ± 4 TMTU 7 ± 0.1 52 ± 1 -72 ± 4 2.6 ± 0.03 56 ± 4 -133 ± 13 DecPt TU 27 ± 0.2 50 ± 1 -74 ± 1 42.1 ± 0.3 53 ± 0.3 -98 ± 1 DMTU 19 ± 0.1 62 ± 1 -39 ± 7 7.0 ± 0.3 69 ± 1 -52 ± 3 TMTU 4 ± 0.3 53± 1 -73 ± 2 4.0 ± 0.04 73 ± 1 -40 ± 4 1
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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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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 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
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 344 and 345: Table S6.9: Average observed rate c
Page 346 and 347: -2304.16 ppm H 3N PPM -2200.0 -2220
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 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
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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 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 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 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
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• prolonged survival in the cell
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