Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
400-300 cm -1): 3308, 3117, 3071 (N–H stretch); 1670 (C=N, pyrimidine group stretch); 1090-1100 (perchlorate counter ion); 450-490 (Pt–N stretch); 315 (Pt–Cl stretch). TOF MS/ES +. (m/z, M 2+): 304 (C2H8N3PtCl species). Anal. Calcd for C4H16N6Cl4O8Pt2: H, 2.00; C, 5.94; N, 10.40. Found: H, 2.08; C, 6.18; N, 10.14%. pdn: Yield: 235.5 mg (0. 291mmol, 35.4%). 1 H NMR (500.5 MHz, D2O), δ /ppm: 9.60, (d, 2H); 8.11, (dd, 2H). 195Pt NMR (107.5 MHz, D2O) δ/ ppm: -2244.82. IR (KBr, 4000-300 cm -1 ): 3303, 3230, 3105 (N–H stretch); 1678 (C=N, pyridazine group stretch); 1090- 1100 (perchlorate counter ion) 333 (Pt–Cl stretch). Anal. Calcd for C4H16N6Cl4O8Pt2: H, 2.00; C, 5.94; N, 10.05. Found: H, 2.00; C, 5.56; N, 9.98%. qzn: Yield: 182.0 mg (0. 212 mmol, 36.0 %). 1H NMR (500.5 MHz, D2O), δ / ppm: 10.16, (s,1H); 10.05, (s, 1H); 9.53, (d, 1H); 8.50, (d, 1H); 8.38, (t, 1H); 8.11, (t,1H). 195 Pt NMR (107.5 MHz, D2O) δ/ ppm: -2321.65, -2345.01. IR (KBr, 4000-300 cm -1): 3285, 3207, 3075 (N–H stretch); 1678 (C=N, quinazoline group stretch); 1090-1100 (perchlorate counter ion); 450-490 (Pt–N stretch); 326 (Pt–Cl stretch). TOF MS/ES +. (m/z, M 2+): 329 (C4H9N3PtCl species). Anal. Calcd for C8H18N6Cl4 O8Pt2: H, 2.11; C, 11.19; N, 9.79. Found: H, 2.47; C, 11.69; N, 9.56%. pht: Yield: 139.7 mg (0.163 mmol, 36.3%). 1 H NMR (500.5 MHZ, D2O), δ/ppm:10.04, (s, 2H); 8.40, (m, 2H); 8.34, (m, 2H). 195Pt NMR (107.5 MHz, D2O) δ/ ppm: -2241.03. IR (KBr, 4000-300 cm -1 ): 3299 (N–H stretch); 1678 (C=N, phthalazine group stretch), 1090-1100 (perchlorate counter ion); 450-490 (Pt–N stretch); 338 (Pt–Cl stretch). TOF MS/ES + . (m/z, M 2+ ): 329 (C4H9N3PtCl species). Anal. Calcd for C8H18N6Cl4O8Pt2: H, 2.11; C, 11.09; N, 9.79. Found: H, 2.25; C, 10.67; N, 9.39%. 5.2.3 Instrumentation and Physical Measurements Microanalysis of C, H, and N was done on a Carlo Erba Elemental Analyzer 1106. The infrared spectra were recorded in the 4000-300 cm -1 range on a Perkin Elmer Spectrum One-FTIR spectrophotometer using KBr pellets. The NMR spectra were measured on a Bruker Avance 500 spectrometer ( 1H, 500 MHz) and ( 195Pt, 107.5 MHz), respectively, at 6
ambient temperature of 30°C. Values of 1H are given in δ (ppm) relative to tetramethylsilane (δ = 0.00) and 195 Pt chemical shifts were externally referenced to K2[PtCl6] in D2O. Mass spectrometric analyses were collected on Hewlett Packard LC-MS using electron impact ionization (ESI-TOF). 5.2.4 Computational Details In an effort to gain further insight into the role of the diazine bridging ligand in such dinuclear Pt(II) complexes, the corresponding diaqua cationic complexes of total charges of 4+ were optimized at the B3LYP/ 33LACVP** (Los Alamos Core Valence pseudo-potentials set) 34 hybrid level, utilizing density functional computation method (DFT), in gaseous phase. B3LYP relates to the hybrid functional Becke’s three parameter formulation 33 which has been proven to be superior to traditional functionals. The Spartan `04 for Windows ® quantum chemical software package was used. 5.2.5 Preparation of the Aqueous Complex Solutions The chloro complexes were converted into aqua analogues in solution by addition of 1.98 equiv. AgClO4 using literature procedure. 35 Since perchlorate ions do not coordinate to Pt(II) the kinetic investigations were studied at pH ca.2.0 to prevent deprotonation of the aqua ligand, 36 and the ionic strength was adjusted to I = 0.10 M (NaClO4 adjusted with perchloric acid). The resultant aqueous solutions were brought to a final complex concentration of 1.34 x 10 -4, 1.0 x 10 -3, 9.20 x 10 -4, 1.79 x 10 -3 and 1.0 x 10 -3 M, respectively, for [{cis–PtOH2(NH3)2}2-–μ–pmn](ClO4)2 (pmn), [{cis– PtOH2(NH3)2}2–μ–pdn](ClO4)2 (pdn), [{cis–PtOH2(NH3)2}2–μ–qzn](ClO4)2 (qzn), [{cis–PtOH2(NH3)2}2–μ–pht](ClO4)2 (pht), and [{cis–PtOH2(NH3)2}2–μ–pzn](ClO4)2 (pzn). A series of nucleophile concentrations in the order: 20, 40, 60, 80 and 100-fold excess of appropriate metal complex concentration, were prepared using the 0.10 M NaClO4/HClO4, at pH ca.2.0. 7
- Page 172 and 173: ln(k 2(1 st ) /T) -3.5 -4.0 -4.5 -5
- Page 174 and 175: Comple x Table 4.4: Summary of Acti
- Page 176 and 177: The decrease in reactivity of 2,6pz
- Page 178 and 179: Table 4.5: DFT calculated (NBO) cha
- Page 180 and 181: eaction proceeds via bimolecular pa
- Page 182 and 183: References 1 T. Storr, K. H.Thomson
- Page 184 and 185: 36 D. Jaganyi, D. Reddy, J.A. Gerte
- Page 186 and 187: Appendix 4 THE INFLUENCE OF THE PYR
- Page 188 and 189: Absorbance at 368. 0 nm 0. 0 8 0. 0
- Page 190 and 191: Table S4.3: Average observed rate c
- Page 192 and 193: k nd obs(2 ) , s-1 0.003 TU DMTU TM
- Page 194 and 195: Table S4.7: Average observed rate c
- Page 196 and 197: Table S4.8: Average observed rate c
- Page 198 and 199: k obs2 , s -1 2.40x10 -4 2.20x10 -4
- Page 200 and 201: Table S4.13: Average observed rate
- Page 202 and 203: Table S4.14: Average observed rate
- Page 204 and 205: Table S4.18: Average observed rate
- Page 206 and 207: k obs(1 st ) , s -1 0.06 0.04 0.02
- Page 208 and 209: Table S4.23: Average observed rate
- Page 210 and 211: ln(k 2(3 rd ) /T) -10.0 -10.5 -11.0
- Page 212 and 213: SpinWorks 2.5: 2,6 pznClO4 in D2O N
- Page 214 and 215: Table of Contents-5 Chapter 5 .....
- Page 216 and 217: List of Tables Table 5.1: A summary
- Page 218 and 219: 5.1 Introduction Multinuclear plati
- Page 220 and 221: onding. For this reason, pKa titrat
- Page 224 and 225: 5.2.6 Spectrophotometric pKa Titrat
- Page 226 and 227: Table 5.1: A summary of DFT-calcula
- Page 228 and 229: However, because the highest occupi
- Page 230 and 231: Table 5.2: Acid dissociation consta
- Page 232 and 233: Table 5.3: A summary of DFT calcula
- Page 234 and 235: H3N 6 eq TU 0 eq TU Ha NH3 Ha Cl TU
- Page 236 and 237: third step due to the trans-effect
- Page 238 and 239: [H 2 O-Pt-(NN)-Pt-OH 2 ] +4 [NU-Pt-
- Page 240 and 241: k obs(1st) / s -1 0.20 TU DMTU TMTU
- Page 242 and 243: thiourea nucleophile is large enoug
- Page 244 and 245: ln(k st 2(1 ) /T) -3 -4 -5 -6 -7 -8
- Page 246 and 247: is the same as the electron-withdra
- Page 248 and 249: associative mode of substitution me
- Page 250 and 251: 16 H. Ertürk, J. Maigut, R. Puchta
- Page 252 and 253: 43 (a) D. Jaganyi, A. Hofmann and R
- Page 254 and 255: 276 nm Absorbance 0 . 6 5 0 . 6 4 0
- Page 256 and 257: k obs(1 st ) , s -1 0.4 0.3 0.2 0.1
- Page 258 and 259: Table S5.5: Average observed rate c
- Page 260 and 261: ln(k 2(2 nd ) /T) -8.0 TU -8.5 -9.0
- Page 262 and 263: pzn PPM -1750.0 -1850.0 -1950.0 -20
- Page 264 and 265: Table S5.9: Average observed rate c
- Page 266 and 267: Figure S5.13: UV/Visible spectra fo
- Page 268 and 269: k obs(1 st ) in s -1 0.030 0.025 0.
- Page 270 and 271: Table S5.17: Average observed rate
400-300 cm -1): 3308, 3117, 3071 (N–H stretch); 1670 (C=N, pyrimidine group stretch);<br />
1090-1100 (perchlorate counter ion); 450-490 (Pt–N stretch); 315 (Pt–Cl stretch). TOF<br />
MS/ES +. (m/z, M 2+): 304 (C2H8N3PtCl species). Anal. Calcd for C4H16N6Cl4O8Pt2: H, 2.00;<br />
C, 5.94; N, 10.40. Found: H, 2.08; C, 6.18; N, 10.14%.<br />
pdn: Yield: 235.5 mg (0. 291mmol, 35.4%). 1 H NMR (500.5 MHz, D2O), δ /ppm: 9.60, (d,<br />
2H); 8.11, (dd, 2H). 195Pt NMR (107.5 MHz, D2O) δ/ ppm: -2244.82. IR (KBr, 4000-300<br />
cm -1 ): 3303, 3230, 3105 (N–H stretch); 1678 (C=N, pyridazine group stretch); 1090-<br />
1100 (perchlorate counter ion) 333 (Pt–Cl stretch). Anal. Calcd for C4H16N6Cl4O8Pt2: H,<br />
2.00; C, 5.94; N, 10.05. Found: H, 2.00; C, 5.56; N, 9.98%.<br />
qzn: Yield: 182.0 mg (0. 212 mmol, 36.0 %). 1H NMR (500.5 MHz, D2O), δ / ppm: 10.16,<br />
(s,1H); 10.05, (s, 1H); 9.53, (d, 1H); 8.50, (d, 1H); 8.38, (t, 1H); 8.11, (t,1H). 195 Pt NMR<br />
(107.5 MHz, D2O) δ/ ppm: -2321.65, -2345.01. IR (KBr, 4000-300 cm -1): 3285, 3207,<br />
3075 (N–H stretch); 1678 (C=N, quinazoline group stretch); 1090-1100 (perchlorate<br />
counter ion); 450-490 (Pt–N stretch); 326 (Pt–Cl stretch). TOF MS/ES +. (m/z, M 2+): 329<br />
(C4H9N3PtCl species). Anal. Calcd for C8H18N6Cl4 O8Pt2: H, 2.11; C, 11.19; N, 9.79. Found:<br />
H, 2.47; C, 11.69; N, 9.56%.<br />
pht: Yield: 139.7 mg (0.163 mmol, 36.3%). 1 H NMR (500.5 MHZ, D2O), δ/ppm:10.04, (s,<br />
2H); 8.40, (m, 2H); 8.34, (m, 2H). 195Pt NMR (107.5 MHz, D2O) δ/ ppm: -2241.03. IR<br />
(KBr, 4000-300 cm -1 ): 3299 (N–H stretch); 1678 (C=N, phthalazine group stretch),<br />
1090-1100 (perchlorate counter ion); 450-490 (Pt–N stretch); 338 (Pt–Cl stretch). TOF<br />
MS/ES + . (m/z, M 2+ ): 329 (C4H9N3PtCl species). Anal. Calcd for C8H18N6Cl4O8Pt2: H, 2.11;<br />
C, 11.09; N, 9.79. Found: H, 2.25; C, 10.67; N, 9.39%.<br />
5.2.3 Instrumentation and Physical Measurements<br />
Microanalysis <strong>of</strong> C, H, and N was done on a Carlo Erba Elemental Analyzer 1106. The<br />
infrared spectra were recorded in the 4000-300 cm -1 range on a Perkin Elmer Spectrum<br />
One-FTIR spectrophotometer using KBr pellets. The NMR spectra were measured on a<br />
Bruker Avance 500 spectrometer ( 1H, 500 MHz) and ( 195Pt, 107.5 MHz), respectively, at<br />
6
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