Chapter 4 - Jacobs University

More documents

Recommendations

Info

<strong>Chapter</strong> 7 Pt-containing Polyoxometalate 7.4 Results and discussion 7.4.1 Synthesis and structure The polyanion [H 2 Pt IV V 9 O 28 ] 5- (5) was prepared by a simple, one-pot stoichiometric reaction of Na 2 [Pt(OH) 6 ] 15 with NaVO 3 in aqueous solution (pH 5.3), and then isolated as the hydrated sodium salt Na 5 [H 2 PtV 9 O 28 ]·21H 2 O (5a). Polyanion 5 has the well-known decavanadate structure, but one of the two central addenda sites is now occupied by platinum(IV) in a regioselective fashion (Figure 7.3). Therefore, 5 represents the first transition-metal-substituted decavanadate derivative and the first platinum (IV)-containing polyoxovanadate. Interestingly, 5 exhibit no disorder of the platinum (IV) ion over any of the remaining eight decavanadate sites (which all have a terminal oxo ligand). This observation indicates that the Pt 4+ ion in 5 favors a coordination environment consisting exclusively of bridging oxo ligands. The bond lengths around the octahedral Pt center are very regular, ranging from 1.980(3) to 2.027(3) Å (see Figure 7.3). The polyanion 5 has idealized C 2v symmetry. Both H atoms attached to 5 (Figure 6.3) were not only identified by bond valence sum (BVS) calculations, 16 but were actually located in the difference Fourier map and refined with the O···H separations restrained to 0.85(10) Å. These protons are particularly important in the solid state as they enforce formation of a dimer assembly, [H 5 (Pt IV V 9 O 28 ) 2 ] 10- , through four inter anion O-H···O hydrogen bonds (see the Supporting Information).We also prepared derivatives of 5 with different degrees of protonation, such as [H x Pt IV V 9 O 28 ] (7-x)- (x = 2.5, 3, 5, 5), as shown by single-crystal X-ray analysis. Considering that the {PtO 6 } octahedron is significantly larger than the other nine {VO 6 } octahedra, we believe that 5 must tolerate some strain. However, our solid-state and solution (see below) results indicate that 5 is rather stable. 129
<strong>Chapter</strong> 7 Pt-containing Polyoxometalate Figure 7.3 a) Polyhedral representation of 5 ({VO 6 } octahedra: light blue). b) Ball-and-stick representation of 5 showing 30% thermal ellipsoids and complete atom labeling. Bond lengths [Å] and angles [ o ]: Pt-Oh1 1.985(3), Pt-Oh2 1.980(3), Pt-Oc3 2.020(3), Pt-Oc5 2.026(3),Pt-Ob7 2.027(3), Pt-Ob8 2.021(3); Oh1-Pt-Ob7 173.1(1), Oh2-Pt-Ob8 173.3(1), Oc3-Pt-Oc5 168.5(1), Oh1-Pt-Oh2 85.3(1), Oh2-Pt-Ob7 Ob7 88.0(1), Oh1-Pt-Ob8 88.1(1), Ob7-Pt-Ob8 Ob8 98.7(1). 130
Page 1 and 2:
Synthesis, Structure and Properties
Page 3 and 4:
"The greatest book of philosophy, w
Page 5 and 6:
system, space group I4/m, unit cell
Page 7 and 8:
Acknowledgements The accomplishment
Page 9 and 10:
teaching, and Professor Maravanji S
Page 11 and 12:
2.1.2 Single crystal X-ray diffract
Page 13 and 14:
5.5 Conclusion…………………
Page 15 and 16:
9.1.6.1 Results and discussion…
Page 17 and 18:
9.3.5 Synthesis of K 12 [Hf 4 (µ 2
Page 19 and 20:
Crespo………………………
Page 21 and 22:
Figure 5.4 ORTEP view of the asymme
Page 23 and 24:
Figure 9.6 31 P NMR of 7a in H 2 O/
Page 25 and 26:
Figure 9.34 TGA spectrum of 17a…
Page 27 and 28:
Figure 9.62 FTIR spectrum of 23a…
Page 29 and 30:
Table 9.6 Crystal data and structur
Page 31 and 32:
Chapter 1 Introduction heteropolyan
Page 33 and 34:
Chapter 1 Introduction 1.3 Structur
Page 35 and 36:
Chapter 1 Introduction C) Keggin a-
Page 37 and 38:
Chapter 1 Introduction shows no suc
Page 39 and 40:
Chapter 1 Introduction α-[P 2 W 18
Page 41 and 42:
Chapter 1 Introduction Figure 1.7 B
Page 43 and 44:
Chapter 1 Introduction [P 2 W 18 O
Page 45 and 46:
Chapter 1 Introduction 1.5.3 Medici
Page 47 and 48:
Chapter 1 Introduction (17) Evans,
Page 49 and 50:
Chapter 1 Introduction (48) Mizuno,
Page 51 and 52:
Chapter 1 Introduction (84) Isabell
Page 53 and 54:
Chapter 2 were block-diagonal least
Page 55 and 56:
Chapter 2 Experimental 2.2.3 Synthe
Page 57 and 58:
Chapter 2 Experimental 2.2.7 Synthe
Page 59 and 60:
Chapter 2 Experimental 2.2.11 Synth
Page 61 and 62:
Chapter 2 Experimental 2.3Reference
Page 63 and 64:
Chapter 3 The Wheel-Shaped Cu 20 in
Page 65 and 66:
Chapter 3 The Wheel-Shaped Cu 20 3.
Page 67 and 68:
Page 69 and 70:
Chapter 3 The Wheel-Shaped Cu 20 Fi
Page 71 and 72:
Chapter 3 The Wheel-Shaped Cu 20 Cu
Page 73 and 74:
Page 75 and 76:
Chapter 3 The Wheel-Shaped Cu 20 20
Page 77 and 78:
Chapter 4 16-Iron Metal Center Nano
Page 79 and 80:
Chapter 4 16-Iron Metal Center Nano
Page 81 and 82: Chapter 4 16-Iron Metal Center Nano
Page 93 and 94: Chapter 5 Organoruthenium POM Chapt
Page 95 and 96: Chapter 5 Organoruthenium POM 5.2 S
Page 97 and 98: Chapter 5 Organoruthenium POM 5.3 X
Page 99 and 100: Chapter 5 Organoruthenium POM 5.4 R
Page 101 and 102: Chapter 5 Organoruthenium POM The f
Page 103 and 104: Chapter 5 Organoruthenium POM On th
Page 105 and 106: Chapter 5 Organoruthenium POM Figur
Page 107 and 108: Chapter 5 Organoruthenium POM (11)
Page 109 and 110: Chapter 6 U-peroxo-Polyoxometalate
Page 127 and 128: Chapter 7 Pt-containing Polyoxometa
Page 131: Chapter 7 Pt-containing Polyoxometa
Page 141 and 142: Chapter 8 Collaborative Work Chapte
Page 143 and 144: Chapter 8 Collaborative Work 8.2.1
Page 145 and 146: Chapter 9 Unpublished Results Figur
Page 147 and 148: Chapter 9 Unpublished Results solid
Page 151 and 152: Chapter 9 Unpublished Results 9.1.3
Page 163 and 164: Chapter 9 Unpublished Results There
Page 173 and 174: Chapter 9 Unpublished Results Table
Page 183 and 184:
Chapter 9 Unpublished Results 9.2.2
Page 185 and 186:
Page 187 and 188:
Chapter 9 Unpublished Results Figur
Page 189 and 190:
Chapter 9 Unpublished Results Table
Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
Page 199 and 200:
Page 201 and 202:
Chapter 9 Unpublished Results exhib
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Chapter 9 Unpublished Results The d
Page 221 and 222:
Page 223 and 224:
Chapter 9 Unpublished Results 23a (
Page 225 and 226:
Page 227 and 228:
Page 229 and 230:
Page 231 and 232:
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Curriculum Vitae SIB SANKAR MAL Dep
Page 239 and 240:
EDUCATION PhD Jacobs University (20
Page 241 and 242:
POSTER, ORAL PRESENTATION 1. Poster
Page 243 and 244:
6. “Two Iron-Containing Tungstoge
Page 245 and 246:
Appendix
Page 247 and 248:
Page 249 and 250:
Appendix
Page 251 and 252:
show all

Chapter 4 - Jacobs University

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?