Dissertation

More documents

Recommendations

Info

|3.3 NN-NHC-Ligand bbip: Toward Second Generation Catalysts| Intensety / a.u. x10 6 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 563.3 810.9 821.9 528.4 1235.1 500 1000 1500 m/z Intensity / a.u. Intensety / a.u. x10 5 5 4 3 2 1 0 2000 1500 1000 500 0 meas. calc. 1232.1 1231.1 1230.1 1229.1 1227.1 1228.1 1230.3 1229.3 1228.3 1227.3 1226.3 1231.3 1235.1 1234.1 1233.1 1235.3 1234.3 1233.3 1232.3 1236.1 1237.1 1238.1 1239.1 1236.3 1237.3 1238.3 +MS, 0.2-1.9min #(5-67) 1240.1 1241.1 1243.0 C63H68N8RuPdCl 2(H3O), M ,1233.32 1239.3 1240.3 1241.3 1242.3 1225 1230 1235 1240 1245 m/z Figure 96: ESI-MS spectrum of Ru(bbip)Pd measured in methanol and representative match of the calculated and measured isotopic patterns of the fragment ions. The main peaks belong to the following fragment ions: m/z = 1235.1, {(tbbpy) 2 Ru(µ-bbip)Pd(H 2 O)Cl 2 } + ; 821.9 {[{(tbbpy)Ru(µ-bbip)} 2 {Pd 2 Cl 4 }][Cl]} 3+ ; 810.9 [{(tbbpy) 2 Ru(µ-bbip)} 2 {Pd 2 Cl 4 }] 3+ ; 563.3 [{(tbbpy) 2 Ru(µ-bbip)} 2 {PdCl 2 }] 4+ ; and 528.4 {[Ru(tbbpy) 2 (bbip)](H 2 O)} 2+ . Rel. Intensety / % 100 80 60 40 20 0 519.4 642.3 1319.3 1463.2 1567.2 500 1000 1500 2000 m/z Intensety / a.u. x10 5 Intensity / a.u. 8 6 4 2 0 2000 1500 1000 500 0 1316.3 1315.3 1313.3 1314.3 1316.4 1315.4 1313.4 1314.4 1317.3 1317.4 1318.3 1318.4 1319.3 1321.3 1319.4 1320.3 1320.4 1321.4 1322.3 1323.3 1322.4 +MS, 4.2-5.6min #(138-183) 1324.3 1325.3 1326.3 1323.4 C71H80N8Cl2RuRh, M ,1319.40 1324.4 1325.4 1326.4 1310.0 1315.0 1320.0 1325.0 1330.0 m/z Figure 97: ESI-MS spectrum of Ru(bbip)Rh measured in methanol and a representative match of the calculated and measured isotopic patterns of the fragment ions. The denoted peaks belong to the following fragment ions: m/z = 1567.2 [{(tbbpy) 2 Ru}(µ-bbip){Rh(cod)Cl} 2 Cl] + , 1463.2 [{(tbbpy) 2 Ru}(µ-bbip){Rh(cod)Cl}{AgCl}Cl] + , 1319.3 [{(tbbpy) 2 Ru}(µ-bbip){Rh(cod)Cl}Cl] + , 642.3 [{(tbbpy) 2 Ru}(µ-bbip){Rh(cod)Cl}] 2+ , 519.4 [Ru(tbbpy) 2 (bbip)] 2+ . a dimeric tetranuclear {Pd 2 Cl 2 }-bridged species (Ru(bbip)Pd-Pd(bbip)Ru) and a monomeric trinuclear {PdCl 2 }-bridged species (Ru(bbip)Pd(bbip)Ru) (see figure 96). |137|
|3.3 NN-NHC-Ligand bbip: Toward Second Generation Catalysts| In addition to the preparation of the palladium complex, the silver precursor was used to synthesize a rhodium-NHC-complex [(tbbpy) 2 Ru(µ-bbip)Rh(cod)Cl] 2+ (Ru(bbip)Rh) using [Rh(cod)Cl] 2 (COD = 1,5-cyclooctadiene) for the transmetalation reaction. Similar work-up gave a red solid compound which was characterized by NMR- and MS-methods. In this case all CH 2 - signals of the benzyl group are shifted with respect to the asymmetric NHC-bound {Rh(cod)Cl}- metal fragment so that all four protons give independent signals with the characteristic 2 J-coupling to the respective geminal proton (δ Ru(bbip)Rh CH 2 (d, 1H, 2 J = 20 Hz) and δ Ru(bbip)Rh CH 2 ” = 7.20 ppm (d, 1H, 2 J = 20 Hz), δ Ru(bbip)Rh CH 2 ’ = 6.75 ppm = 7.05 ppm (d, 1H, 2 J = 20 Hz), δ Ru(bbip)Rh CH 2 ”’ = 6.95 ppm (d, 1H, 2 J = 20 Hz), see figure 95) in contrast to the silver complex (δ Ru(bbip)Ag CH 2 = 6.50 ppm, (s, 4H)). Additionally, it was possible to identify the COD-related signals which further supported the formation of the desired compounds. Mass spectrometric analysis revealed the characteristic pattern (for details see figure 97) which correspond to the calculated isotopic patterns for the expected binuclear complex Ru(bbip)Rh. Furthermore, unexpected peaks which refer to AgCl-adducts and Rh(cod)Cladducts of Ru(bbip)Rh were found. It was concluded that undesired soluble [AgCl 2 ] − or higher AgCl-cluster counter ions which did not precipitate from the solution were still present in the product, which is a common problem in transmetalation reactions with formation of silver halogenides. [188, 191] Unfortunately, it was not possible to remove the impurities from the mixture by further work up steps such as dissolving the complex in dichloromethane and reprecipitation with diethyl ether. Counter ion exchange with a [PF 6 ]-salt did not succeed. 3.3.8 Spectroscopic Characterization For the series of this new ruthenium chromophores photophysical properties were determined. Special interest was placed on the influence of the electronic transformations at the imidazole moiety in the N,N’-coordinated ruthenium complexes with the new ip-type ligands. Preliminary insights were derived from steady-state absorption and emission studies in dichloromethane and acetonitrile (see figures 98 and 99, compare table 14 on page 143). At first glance, all described complexes show the typical broad 1 MLCT absorption between 400 and 500 nm which give rise to similar 3 MLCT emission in the 550 to 800 nm range (for an example see figure 98). [36] Upon closer analysis, however, subtle changes become visible as the ligand |138|
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:
|3.2 Bisphenanthroline: A Suitable
Page 98 and 99: |3.2 Bisphenanthroline: A Suitable
Page 104 and 105: f f f f f f |3.2 Bisphenanthroline:
Page 122 and 123: |3.3 NN-NHC-Ligand bbip: Toward Sec
Page 170 and 171: |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 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
|6.2 Synthesis of the Metal Complex
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:
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?