Tuning Reactivity of Platinum(II) Complexes
Tuning Reactivity of Platinum(II) Complexes Tuning Reactivity of Platinum(II) Complexes
SpinWorks 2.5: 2,6 pznClO4 in D2O NH 3 C l Pt NH 3 NH 3 N N P t C l 2+ NH 3 -2322.7 PPM -2220.0 -2240.0 -2260.0 -2280.0 -2300.0 -2320.0 -2340.0 -2360.0 -2380.0 -2400.0 -2420.0 -2440.0 -2460.0 -2480.0 -2500.0 -2520.0 -2540.0 -2560.0 -2580.0 66 -2464.16 Figure S4.26: The 107 MHz 195 Pt NMR spectrum of [cis–{PtCl(NH3)2}2–µ– 2,6pzn](ClO4)2 showing Pt1N3Cl and Pt2N3Cl coordination Pt labels are as defined in Scheme 4.1. 2,3pzn PPM -1750.0 -1850.0 -1950.0 -2050.0 -2150.0 -2250.0 -2350.0 -2450.0 -2550.0 -2650.0 -2750.0 file: C:\Documents and Settings\205526966.CHEMLIB1.044\Desktop\po_c23pzn_195Pt.nmr5\1\fid expt: < zg> transmitter freq.: 107.249647 MHz time domain size: 124986 points width: 125000.00 Hz = 1165.505006 ppm = 1.000112 Hz/pt number of scans: 2229 -2314.3 freq. of 0 ppm: 107.486208 MHz processed size: 65536 complex points LB: 50.000 GB: 0.0000 Figure S4.27: The 107 MHz 195Pt NMR spectrum of [cis–{PtCl(NH3)2}2–µ– 2,3pzn](ClO4)2.
Figure S29: Mass spectrum for complex 2,5pzn (m/e, M 2+) Figure S30 Mass spectrum for complex 2,3pzn (m/e, M 2+ ) 67
- Page 162 and 163: electrophilicity and acidity of the
- Page 164 and 165: (A) 18 Absorbance 0.08 0.07 0.06 0.
- Page 166 and 167: k obs(3 rd ) , s -1 -5 6.00x10 TMTU
- Page 168 and 169: 4.3.4 Kinetics with NMR The substit
- Page 170 and 171: ln([ML] t ) 4.0 3.5 3.0 2.5 2.0 1.5
- 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 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 222 and 223: 400-300 cm -1): 3308, 3117, 3071 (N
- 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
Figure S29: Mass spectrum for complex 2,5pzn (m/e, M 2+)<br />
Figure S30 Mass spectrum for complex 2,3pzn (m/e, M 2+ )<br />
67
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