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|3.3 NN-NHC-Ligand bbip: Toward Second Generation Catalysts| Figure 92: ORTEP drawing of the solid state structures of Ru(ip) (left) and Ru(bip) (right). Ellipsoids were drawn at the 70% probability level, counter ions, solvent molecules, and hydrogen atoms except for the imidazole moieties were omitted for clarity. and angles from the N,N’-chelating site and from the imidazole/carbene site will be discussed. With respect to the phenanthroline coordination site, all complexes exhibit a number of typical similarities which can be found in other ruthenium bipyridine/phenanthroline-type complexes as well. The Ru-N1 and Ru-N2 bond distances vary in a narrow range between 2.055(4) Å and 2.067(5) Å. Even in the complex Ru(bbip) no significant influence on the Ru-N distances was found although it bears a positively charged ligand. Furthermore, the resulting N1-Ru-N2 angle varies insignificantly between 79.18(16)° and 80.15(17)° in all complexes of this series. The coordination environment with respect to the nearby bond lengths and angles remains unaffected by the changes at the imidazole part of the ligands. Thus, the N1-C12 bond lengths and N2-C11 bond lengths vary between 1.363(7) Å and 1.385(7) Å and the C11-C12 distances vary between 1.421(8) Å and 1.449(7) Å, respectively. In the N1-C12-C11 and the N2-C11-C12 bond angles only minor variations between 115.1(5)° and 117.4(5)° were observed. Comparison of the N,N’-coordination site in series of ruthenium complexes and in the respective pre-ligands revealed no or only very slight (not in every case significant) changes in the corresponding distances and angles. The tendency goes toward more acute N1-C11- C12 / N2-C12-C11 angles (e.g. ∠ ip (N2,C12,C11) = 117.0(2)° ≥ ∠Ru(ip) (N2,C12,C11) = 115.8(5)°), longer C12-N1 / C11- N2 bond lengths (e.g. d ip Ru(ip) (N2-C11) = 1.360(3) Å < d(N2-C11) = 1.385(5) Å) and shorter C11-C12 distances |131|
|3.3 NN-NHC-Ligand bbip: Toward Second Generation Catalysts| Figure 93: ORTEP representation of the molecular Structure of Ru(bbip) (top) and Ru(bbip)Ag (bottom). Anions, solvent molecules and protons were omitted from the X-ray structures for clarity. (e.g. d bip Ru(bip) (C11-C12) = 1.463(3) Å > d(C11-C12) = 1.421(8) Å) in the ruthenium complexes. Comparison of the changes in the imidazole ring of this series reflect the performed changes. It can be expected that a certain degree of asymmetry is present in the imidazole rings of Ru(ip) and Ru(bip) due to the contribution of the resonance structures with a double bond between C13 and N4. Furthermore, a stepwise increase of the π-character of the carbene carbon and a stepwise decrease of the π-delocalization on the imidazole rings can be expected with respect to the starting imidazole Ru(bip) and transformation into the imidazolium salt Ru(bbip) and subsequent carbene complex formation. |132|
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Development of Novel Catalysts for
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Diese Arbeit entstand auf Anregung
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Den Arbeisgruppen von Prof. Dr. U.
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Contents 1 Introduction 1 1.1 Fossi
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|Contents| 6 Experimental Section 1
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|1 Introduction| 1 Introduction The
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|1.1 Fossil Fuels and Nuclear Power
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|1.2 Renewable Fuels| of natural ga
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|1.3 Energy Transformation and Stor
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|1.4 Solar Energy Conversion| A fra
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|1.5 Photosynthesis| Figure 9: Mole
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|1.6 Photocatalyzed Reactions| 2 NA
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|1.6 Photocatalyzed Reactions| (1)
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|1.7 Mimicking Photosynthesis| So t
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|1.8 Formalisms of Photocatalytic S
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|1.9 Multicomponent Systems from Fu
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|1.10 Intramolecular Photoredoxcata
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|2 Scope of the Thesis| motifs with
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|3.1 Brominated Phenanthrolines - A
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Page 92 and 93: |3.1 Brominated Phenanthrolines - A
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Page 185 and 186: |4 Summary| 4 Summary Against the b
Page 187 and 188: |4 Summary| The resulting complexes
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Page 191 and 192: |4 Summary| absorption between 430
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|4 Summary| additional NN- and NHC-
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|5 Zusammenfassung| Die Herstellung
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|5 Zusammenfassung| phenphen und Ru
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|5 Zusammenfassung| Fragment tragen
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|5 Zusammenfassung| [TEA] + TEA vis
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|5 Zusammenfassung| In einer abschl
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|6 Experimental Section| Spectroele
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|6 Experimental Section| 1.3648 was
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|6.1 Synthesis of the Organic Ligan
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|6.2 Synthesis of the Metal Complex
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|7 Appendix| 7 Appendix dd ddd DEI
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|7 Appendix| Ru(tpphz)Os [Ru(bpy) 2
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|References| [26] M. Chanon, M. Sch
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|References| [81] S. Tschierlei, M.
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|References| [138] L. Pazderski, J.
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|References| [194] C. Liu, J. Li, B
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Selbstständigkeitserklärung: Ich
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