Dissertation

More documents

Recommendations

Info

|3.4 Outlook, Exploratory Investigations and Perspectives| Table 16: Selected bond lengths [Å] and angles [°] of new ligands and complexes with imidazophenanthroline backbone. bond length [Å] or angle [°] eip Ru(eip) edip Ru(Br 2 bip) Ru1 - N1 2.060 (5) 2.054 (5) Ru1 - N2 2.062 (5) 2.064 (6) N4 - C13 1.314 (4) 1.269 (10) 1.323 (8) 1.319 (10) N3 - C13 1.361 (3) 1.361 (9) 1.320 (7) 1.345 (10) N3 - C5 1.384 (3) 1.390 (8) 1.389 (7) 1.380 (9) N4 - C6 1.385 (3) 1.385 (8) 1.402 (7) 1.379 (10) C5 - C6 1.379 (4) 1.385 (8) 1.374 (8) 1.390 (10) N1 - C12 1.353 (3) 1.386 (7) 1.366 (7) 1.362 (9) N2 - C11 1.360 (3) 1.361 (8) 1.359 (7) 1.370 (9) N1 - C1 1.315 (3) 1.332 (8) 1.319 (8) 1.324 (9) N2 - C10 1.327 (3) 1.321 (8) 1.314 (8) 1.328 (10) C11 - C12 1.477 (4) 1.447 (8) 1.451 (9) 1.443 (10) N1 - Ru1 - N2 80.0 (2) 79.5 (2) N3 - C13 - N4 113.9 (3) 114.5 (6) 110.8 (5) 114.7 (7) C13 - N3 - C5 105.9 (2) 105.7 (6) 107.6 (5) 106.3 (6) C13 - N4 - C6 103.7 (2) 104.0 (6) 108.2 (5) 102.9 (6) N3 - C5 - C6 105.3 (2) 104.8 (5) 107.8 (5) 104.7 (6) N4 - C6 - C5 111.1 (2) 110.9 (6) 105.6 (5) 111.4 (6) N1 - C12 - C11 117.2 (2) 115.1 (5) 117.1 (5) 115.6 (6) N2 - C11 - C12 117.4 (2) 117.4 (5) 116.4 (5) 116.0 (6) C1 - N1 - C12 117.6 (2) 118.0 (5) 119.4 (5) 118.2 (6) C10 - N2 - C11 117.2 (2) 117.2 (5) 117.9 (5) 118.5 (6) Comparison of the N,N’-donor site in the ruthenium complex and in the respective pre-ligand eip revealed only very slight (not in every case significant) changes in the corresponding distances and angles, which are mainly located at the phenanthroline site. The tendency goes toward more acute N1-C11-C12 / N2-C12-C11 angles (e.g. ∠ eip (N2,C12,C11) = 117.2(2)° ≥ ∠Ru(eip) (N2,C12,C11) = 115.1(0)°), shorter C12- N1 / C11-N2 bond lengths (e.g. d eip Ru(eip) (N1-C12) = 1.353(3) Å < d(N1-C12) = 1.386(7) Å) and longer C11-C12 distances (e.g. d eip Ru(eip) (C11-C12) = 1.477(4) Å > d(C11-C12) = 1.447(8) Å) in the ruthenium complexes, which is consistent with the changes that generally occur in such systems upon ruthenium coordination. |171|
|3.4 Outlook, Exploratory Investigations and Perspectives| As described for Ru(bbip),a transformation of the imidazolium salt into the corresponding carbene derivatives of different metal centers is very important. For the subsequent use as starting material in the transmetallation reactions, formation of the NHC-silver complex of Ru 2 (edip) became interesting at this stage. In this context method C2 was applied, using Ag 2 O as base for the transformation of the imidazolium salt into the corresponding metal-NHC complex (see figure 123) as discribed for Ru(bbip). N N N N Ru 2+ N N N N N N N N N Ru 2+ N N N Ru 2 (edip) Ag 2 O method C2 N N N N Ru 2+ N N N N Cl Ag Cl Ag N N N N N Ru 2+ N N N Ru 2 (edip)Ag 2 Figure 123: Preparation of the tetranuclear heterobimetallic silver NHC-complex of Ru 2 (edip). To increase the driving force the chloride salt of Ru 2 (edip) was prepared. Counter ion exchange of the [PF 6 ]-salt of Ru 2 (edip) with (Bu) 4 NCl in acetone/ethyl acetate gave the corresponding chloride salt in quantitative yield. The complexation reaction was carried out in dichloromethane. After stirring Ru 2 (edip) and Ag 2 O in the presence of molecular sieves in dichloromethane for 16 hours, the solids were filtered off and the volatiles were removed from the remaining solution. Analysis of the remaining solid gave clear evidence for a complete conversion into the pure product [{(tbbpy) 2 Ru} 2 (µ-edip){AgCl} 2 ]Cl 4 (Ru 2 (edip)Ag 2 ). The disappearance of the |172|
Page 1 and 2:
Development of Novel Catalysts for
Page 3 and 4:
Diese Arbeit entstand auf Anregung
Page 5 and 6:
Den Arbeisgruppen von Prof. Dr. U.
Page 7 and 8:
Contents 1 Introduction 1 1.1 Fossi
Page 9 and 10:
|Contents| 6 Experimental Section 1
Page 12 and 13:
|1 Introduction| 1 Introduction The
Page 14 and 15:
|1.1 Fossil Fuels and Nuclear Power
Page 16 and 17:
|1.2 Renewable Fuels| of natural ga
Page 18 and 19:
|1.3 Energy Transformation and Stor
Page 20 and 21:
|1.4 Solar Energy Conversion| A fra
Page 22 and 23:
|1.5 Photosynthesis| Figure 9: Mole
Page 24 and 25:
|1.6 Photocatalyzed Reactions| 2 NA
Page 26 and 27:
|1.6 Photocatalyzed Reactions| (1)
Page 28 and 29:
|1.7 Mimicking Photosynthesis| So t
Page 30 and 31:
|1.8 Formalisms of Photocatalytic S
Page 32 and 33:
|1.9 Multicomponent Systems from Fu
Page 34 and 35:
Page 36 and 37:
Page 38 and 39:
Page 40 and 41:
Page 42 and 43:
Page 44 and 45:
Page 46 and 47:
Page 48 and 49:
Page 50 and 51:
Page 52 and 53:
|1.10 Intramolecular Photoredoxcata
Page 54 and 55:
Page 56 and 57:
Page 58 and 59:
Page 60 and 61:
Page 62 and 63:
Page 64 and 65:
|2 Scope of the Thesis| motifs with
Page 66 and 67:
|3.1 Brominated Phenanthrolines - A
Page 68 and 69:
Page 70 and 71:
Page 72 and 73:
Page 74 and 75:
Page 76 and 77:
Page 78 and 79:
Page 80 and 81:
Page 82 and 83:
Page 84 and 85:
Page 86 and 87:
Page 88 and 89:
Page 90 and 91:
Page 92 and 93:
Page 94 and 95:
|3.2 Bisphenanthroline: A Suitable
Page 96 and 97:
Page 98 and 99:
Page 100 and 101:
Page 102 and 103:
Page 104 and 105:
f f f f f f |3.2 Bisphenanthroline:
Page 106 and 107:
Page 108 and 109:
Page 110 and 111:
Page 112 and 113:
Page 114 and 115:
Page 116 and 117:
Page 118 and 119:
Page 120 and 121:
Page 122 and 123:
|3.3 NN-NHC-Ligand bbip: Toward Sec
Page 124 and 125:
Page 126 and 127:
Page 128 and 129:
Page 130 and 131:
Page 132 and 133: |3.3 NN-NHC-Ligand bbip: Toward Sec
Page 170 and 171: |3.4 Outlook, Exploratory Investiga
Page 181: |3.4 Outlook, Exploratory Investiga
Page 185 and 186: |4 Summary| 4 Summary Against the b
Page 187 and 188: |4 Summary| The resulting complexes
Page 189 and 190: |4 Summary| 10 [TEA] + TEA visible
Page 191 and 192: |4 Summary| absorption between 430
Page 193 and 194: |4 Summary| additional NN- and NHC-
Page 195 and 196: |5 Zusammenfassung| Die Herstellung
Page 197 and 198: |5 Zusammenfassung| phenphen und Ru
Page 199 and 200: |5 Zusammenfassung| Fragment tragen
Page 201 and 202: |5 Zusammenfassung| [TEA] + TEA vis
Page 203 and 204: |5 Zusammenfassung| In einer abschl
Page 205 and 206: |6 Experimental Section| Spectroele
Page 207 and 208: |6 Experimental Section| 1.3648 was
Page 209 and 210: |6.1 Synthesis of the Organic Ligan
Page 223 and 224: |6.2 Synthesis of the Metal Complex
Page 233 and 234:
|6.2 Synthesis of the Metal Complex
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Page 241 and 242:
Page 243 and 244:
Page 245 and 246:
Page 247 and 248:
Page 249 and 250:
|7 Appendix| 7 Appendix dd ddd DEI
Page 251 and 252:
|7 Appendix| Ru(tpphz)Os [Ru(bpy) 2
Page 253 and 254:
|References| [26] M. Chanon, M. Sch
Page 255 and 256:
|References| [81] S. Tschierlei, M.
Page 257 and 258:
|References| [138] L. Pazderski, J.
Page 259 and 260:
|References| [194] C. Liu, J. Li, B
Page 261:
Selbstständigkeitserklärung: Ich
show all

Dissertation

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

Delete template?

Save as template?