Tuning Reactivity of Platinum(II) Complexes

More documents

Recommendations

Info

Publications and Conference Contributions Publications Parts of the work reported in Chapters 3 & 4 of the thesis have been published in Dalton Transactions, while the rest are ready for submission for publication. 1. Peter Ongoma and Deogratius Jaganyi, The π-Acceptor Effect in the Substitution Reactions of Tridentate N-Donor Ligand Complexes of Platinum(II): A Detailed Kinetic and Mechanistic study, Dalton Trans., 2012, 41, 10724-10730. 2. Peter O. Ongoma and Deogratius Jaganyi, Mechanistic Elucidation of Linker and Ancillary Ligand Substitution Reactions in Pt(II) Dinuclear Complexes, Dalton Trans, DOI: 10.1039/C2DT31956J. 3. Peter O. Ongoma and Deogratius Jaganyi, Substitution Reactions in Dinuclear Platinum(II) Complexes: an Evaluation of the influence of the Diazine-bridge on Reactivity (Submitted to Dalton Transactions). 4. Peter O. Ongoma and Deogratius Jaganyi, Tuning Reactivity of Platinum (II) complexes with parametalated Pyridine Spacer groups: a kinetic and Mechanistic Study (Submitted to International Journal of Chemical Kinetics) 5. Peter O. Ongoma and Deogratius Jaganyi, The Influence of α,ω- diaminealkane Linker on Ligand Substitution of Pt(II) Dinuclear Complexes: A Thermodynamic and Kinetic Study (Submitted to Transition Metal Chemistry) Poster Presentation 39 th Convention of South Africa Chemical Institute, University of Stellenbosch, South Africa, 30 November to 5 December 2008, entitled: The Role of extended π- conjugation on Substitution Reactions of Pt(II) complexes with Tridentate N-donor ligands. xxii
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 and 24: List of Tables Table 2.1 A selectio
Page 25 and 26: Table 6.4 Summary of rate constants
Page 27: TU thiourea DMTU 1,3-dimethyl-2-thi
Page 31 and 32: Figure 1.4: DNA-adduct formation wi
Page 33 and 34: 1.2.1 Chemotherapy In cancer, a che
Page 35 and 36: stable bonds with N-donor ligands i
Page 37 and 38: Figure 1.3: Intracellular hydrolysi
Page 39 and 40: Coordination of the platinum comple
Page 41 and 42: adducts in proteins and therefore a
Page 43 and 44: one side of the coordination square
Page 45 and 46: spectator tridentates (N-donor chel
Page 47 and 48: comparison of the reactions between
Page 49 and 50: and thermodynamic properties of mon
Page 51 and 52: References 1 E. M. Walker and S. M.
Page 53 and 54: 31 M. Kotowski and R. Van Eldik, In
Page 55 and 56: Endocr. Metab. Invest. Drugs, 1999,
Page 57 and 58: 90 N. Farrel and S. Spinelli, Dinuc
Page 59 and 60: List of Figures Figure 2.1: Structu
Page 61 and 62: Chapter Two 2.0 Ligand Substitution
Page 63 and 64: 2.2 Mechanism of Ligand Substitutio
Page 65 and 66: In a dissociation mechanism the tra
Page 67 and 68: 2.2.3 The Interchange Mechanism (I)
Page 69 and 70: = (k2[B]o + k-2) ([A]t- [A]eq) (2.1
Page 71 and 72: L L M L Y X k -2 k 2 L Solvent L L
Page 73 and 74: d[M]/dt = k 2 [M...B] # 13 (2.17) b
Page 75 and 76: pressure on a reaction mixture. 15,
Page 77 and 78: Time/s Reactions involving breaking
Page 79 and 80:
Figure 2.5: A schematic diagram of
Page 81 and 82:
2.4.2 UV-Visible Spectrophotometry
Page 83 and 84:
[X and [Y ] = initial concentration
Page 85 and 86:
trans-[Pt(py) 2 Cl 2 ] + Y n trans-
Page 87 and 88:
Figure 2.9: Rates of Pt(II) complex
Page 89 and 90:
Table 2.2: The effect of the leavin
Page 91 and 92:
Table 2.3: Rate constants for the s
Page 93 and 94:
destabilisation. It is suggested th
Page 95 and 96:
the complex, where k2(Cl)[ 36Cl ¯]
Page 97 and 98:
inductive donor capacity and weak
Page 99 and 100:
shown in Figure 2.12 (b).The overal
Page 101 and 102:
18 U. Belluco, L. Cattallini, F. Ba
Page 103 and 104:
51 O. F .Wendt and L. I. Elding, J.
Page 105 and 106:
List of figures Figure 3.1 DFT-calc
Page 107 and 108:
Leishmania parasites in addition to
Page 109 and 110:
adjusted by addition of 0.01 M LiCl
Page 111 and 112:
3.2.1.3 Synthesis of Dichloro(1,5-c
Page 113 and 114:
3.2.1.5 Synthesis of [Pt{4’-(2’
Page 115 and 116:
C H 3 I H O II O III O CH 3 N 10 O
Page 117 and 118:
a coupled temperature control unit.
Page 119 and 120:
Table 3.1: Summary of DFT-calculate
Page 121 and 122:
N N Pt Cl + NU N Pt NU + Cl N + whe
Page 123 and 124:
k obs in (s -1 ) k in (s obs -1 ) 9
Page 125 and 126:
The second order rate constant, k2,
Page 127 and 128:
The electronic absorption spectra o
Page 129 and 130:
3.5 Conclusion This study has demon
Page 131 and 132:
15 D. Jaganyi, K-L, De Boer, J-A. G
Page 133 and 134:
Appendix 3 A summary of wavelengths
Page 135 and 136:
k obs (S -1 ) 0.5 0.4 0.3 0.2 0.1 P
Page 137 and 138:
Table S3.2b: Average observed rate
Page 139 and 140:
Table S3.4b: Temperature dependence
Page 141 and 142:
Table S3.7: Average observed rate c
Page 143 and 144:
Table of Contents-4 CHAPTER 4 .....
Page 145 and 146:
ppm. These spectra are indicative o
Page 147 and 148:
CHAPTER 4 Substitution of Aqua Liga
Page 149 and 150:
coordination of sulphur nucleophile
Page 151 and 152:
4.2.2 Synthesis of compounds A tota
Page 153 and 154:
(2,3pzn) Yield: 137.2 mg (58.8 %).
Page 155 and 156:
4.2.7 Determination of pKa values o
Page 157 and 158:
Complex Structure HOMO LUMO pzn D2h
Page 159 and 160:
of the σ-electron donating methyl
Page 161 and 162:
Inspection of the data in Table 4.2
Page 163 and 164:
NH3 NH3 OH2 OH2 k1 k1 NH3 NH3 NU Pt
Page 165 and 166:
k st obs(1 ) , s-1 0.04 0.03 0.02 0
Page 167 and 168:
Table 4.3: Summary of second order
Page 169 and 170:
Figure 4.9: 195Pt NMR spectra of th
Page 171 and 172:
ppm shown as E corresponds to [Pt(T
Page 173 and 174:
ln(K 2(3 rd ) /T) -9.5 -10.0 -10.5
Page 175 and 176:
4.5 Discussion By introducing the m
Page 177 and 178:
pzn 2,3pzn 2,5pz 2,6pzn Figure 4.14
Page 179 and 180:
the number of sulphur bound molecul
Page 181 and 182:
with the weaker σ-donor ability of
Page 183 and 184:
19 (a) V. X. Jin, S. I. Tan and J.
Page 185 and 186:
50 M. E. Oehlsen, A. Hegmans, Y. Qu
Page 187 and 188:
276 nm 0 2 4 6 8 10 1 2 10, T = 25
Page 189 and 190:
Table S4.1: Summary of the waveleng
Page 191 and 192:
k obs(1 st ) , s -1 0.4 0.3 0.2 0.1
Page 193 and 194:
Page 195 and 196:
ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0
Page 197 and 198:
Table S4.10: Average observed rate
Page 199 and 200:
Page 201 and 202:
ln(k 2(2 nd ) /T) -5.0 TU -5.5 -6.0
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
k obs(3 rd ) in s -1 1.0x10 -4 8.0x
Page 209 and 210:
ln(k 2(1 st ) /T) -3.5 TU -4.0 -4.5
Page 211 and 212:
pzn PPM -1750.0 -1850.0 -1950.0 -20
Page 213 and 214:
Figure S29: Mass spectrum for compl
Page 215 and 216:
Figure 5.3: 1H NMR spectra of the r
Page 217 and 218:
Chapter 5 Substitution Reactions in
Page 219 and 220:
nucleophiles. 23 What's more is tha
Page 221 and 222:
(pht, 99%), including sodium perchl
Page 223 and 224:
ambient temperature of 30°C. Value
Page 225 and 226:
5.2.8 Properties of the Ligands Bef
Page 227 and 228:
Structure HOMO LUMO pzn (D2h) pmn (
Page 229 and 230:
[H 2 O -P t-(N N )-P t-O H 2 ] 4 +
Page 231 and 232:
enzodiazine ring. This is supported
Page 233 and 234:
The proton resonances for the coord
Page 235 and 236:
H a H`a Equivalnt to that of free l
Page 237 and 238:
Absorbance 0.125 0.120 0.115 0.110
Page 239 and 240:
Page 241 and 242:
k obs(3rd) / s -1 2.40x10 -4 2.00x1
Page 243 and 244:
Table 5.5: Summary of Activation pa
Page 245 and 246:
ln(k 2(3 rd ) /T) -11.5 -12.0 -12.5
Page 247 and 248:
Comparing the reactivity of qzn aga
Page 249 and 250:
References 1 N. J. Wheate and J. G.
Page 251 and 252:
30 D. Donghi, G. D`Alfonso, M. Maur
Page 253 and 254:
Appendix 5 Comparative Rates of Lig
Page 255 and 256:
Page 257 and 258:
k obs(2 nd ) , s -1 0.003 TU DMTU T
Page 259 and 260:
Page 261 and 262:
SpinWorks 2.5: C-PZN in H2O/D2O NH
Page 263 and 264:
Figure S5.10: UV/Visible spectra fo
Page 265 and 266:
Page 267 and 268:
Page 269 and 270:
k obs(2 nd ) in s -1 0.0012 0.0008
Page 271 and 272:
Page 273 and 274:
ln(k rd 2(3 ) /T) -13 -14 -15 -16 -
Page 275 and 276:
NH 3 NH 3 N N Hb Pt Pt Cl Cl Ha Cl
Page 277 and 278:
k obs(2nd) / s -1 7.00x10 -4 6.00x1
Page 279 and 280:
Page 281 and 282:
ln(k nd 2(2 ) /T) -6.5 -7.0 -7.5 -8
Page 283 and 284:
SpinWorks 2.5: znPt(II)-OP3 in D2O
Page 285 and 286:
Figure S5.30: Mass spectrum for [ci
Page 287 and 288:
Page 289 and 290:
k nd obs(2 ) , in s-1 0.0004 0.0003
Page 291 and 292:
Page 293 and 294:
ln(k nd 2(2 ) /T) -8 -9 -10 -11 -12
Page 295 and 296:
SpinWorks 2.5: phePt(II)-OP1 in D2O
Page 297 and 298:
Table of Contents-6 List of Figures
Page 299 and 300:
iii
Page 301 and 302:
structure as well as the nucleophil
Page 303 and 304:
een determined for the two aqua lig
Page 305 and 306:
Ligand 4,4’-dipyridylmonosulphide
Page 307 and 308:
corrections due to dilution, a larg
Page 309 and 310:
Absorbance 0.18 0.16 0.14 0.12 0.10
Page 311 and 312:
The DFT calculations also reveal th
Page 313 and 314:
Structure HOMO LUMO Pt1 (C2v) Pt2 (
Page 315 and 316:
pyridyl protons Ha/Hb used to monit
Page 317 and 318:
(a) (b) Absorbance 0.26 0.24 0.22 0
Page 319 and 320:
k obs(2nd) , s -1 0.0006 SCN TU DMT
Page 321 and 322:
Table 6.4: Summary of rate constant
Page 323 and 324:
ln(k 2/2 nd)/T) -8.0 -8.2 -8.4 -8.6
Page 325 and 326:
6.4.2 Ligand Substitution Based on
Page 327 and 328:
A further observation is that the s
Page 329 and 330:
References 1 R. E., J. Cummings, A.
Page 331 and 332:
43; (c) E. I. Montero, J. Zhang, J.
Page 333 and 334:
Appendix 6 Table S6.1: Summary of t
Page 335 and 336:
k obs(2 nd ) in s -1 0.00015 TU SCN
Page 337 and 338:
Table S6.5(b): Average observed rat
Page 339 and 340:
Figure S6.6: 195Pt NMR spectrum of
Page 341 and 342:
Page 343 and 344:
Table S6.8(a): Average observed rat
Page 345 and 346:
ln(k 2(2 nd ) /T) -4 -5 -6 -7 -8 -9
Page 347 and 348:
35 30 25 %T 20 15 10 5 0.0 3842 373
Page 349 and 350:
Table S6.12(a): Average observed ra
Page 351 and 352:
Figure S6.19: 195 Pt NMR spectrum o
Page 353 and 354:
Figure S6.23: 1H NMR spectrum of 4,
Page 355 and 356:
Table of Contents-7 Chapter 7 .....
Page 357 and 358:
Chapter 7 The Influence of α,ω-Di
Page 359 and 360:
interstrand and intrastrand DNA add
Page 361 and 362:
7.2.1 Synthesis of Pt(II) Compounds
Page 363 and 364:
(OctPt) Yield: 65.0 mg (29.6%). 1 H
Page 365 and 366:
7.2.8 pKa Titrations of the Diaqua
Page 367 and 368:
Table 7.1: Summary of selected DFT-
Page 369 and 370:
E n e rg y / e V -1 0 .0 -1 2 .0 -1
Page 371 and 372:
differences in the pKa values due t
Page 373 and 374:
NH 3 Cl Ha Hc 2 4 Pt H N 2 1 3 NH 3
Page 375 and 376:
t (h) 12.0 5.0 1.0 0.5 0.0 A 6 eq.
Page 377 and 378:
a 21 Absorbance 0.44 0.42 0.40 0.38
Page 379 and 380:
Page 381 and 382:
ln(k 2(2nd) /T) -8 -9 -10 -11 -12 -
Page 383 and 384:
introduction of a greater number of
Page 385 and 386:
with S-donor nucleophiles. This fin
Page 387 and 388:
18 S. Komeda, G. V. Kalayda, M. Lut
Page 389 and 390:
47 (a) Y. Kasherman, S. Sturup and
Page 391 and 392:
Table S7.3: Summary of kobs(2 nd ),
Page 393 and 394:
Page 395 and 396:
Table S7.6: Summary of kobs(1 st ),
Page 397 and 398:
Page 399 and 400:
Absorbance 1.5 1.0 0.5 0.0 Absorban
Page 401 and 402:
k obs(2 nd ) , in s -1 0.0005 TU DM
Page 403 and 404:
ln(k nd 2(2 ) /T) -9 -10 -11 -12 0.
Page 405 and 406:
Table S7.14: Summary of kobs(1 st )
Page 407 and 408:
Page 409 and 410:
Figure S7.21: 195 Pt NMR for HexPt-
Page 411 and 412:
Table S7.19: Summary of kobs(2 nd )
Page 413 and 414:
Figure S7.25: Mass spectra for OctP
Page 415 and 416:
k nd obs(2 ) , in s-1 0.0008 0.0006
Page 417 and 418:
ln(k nd 2(2 ) /T) -8.5 -9.0 -9.5 -1
Page 419 and 420:
1 NH 3 NH 3 Pt Cl N H 2 NH 2 Pt PPM
Page 421 and 422:
Figure S7.35: Mass spectrum for Dec
Page 423 and 424:
compared to CH3PhPtCl. The “unusu
Page 425 and 426:
process is accelerated by protonati
Page 427 and 428:
of water ligands, was the release o
show all

Tuning Reactivity of Platinum(II) Complexes

Create successful ePaper yourself

Delete template?

Save as template?