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|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| after removal of the ethanol a solution of NH 4 PF 6 was added to exchange the chloride ions and to precipitate the desired product from the reaction mixture. Application of this procedure yielded [Ru(tbbpy) 2 (phenBr)] 2+ (Ru(phenBr)) and [Ru(tbbpy) 2 (phenBr 2 )] 2+ (Ru(phenBr 2 )) in high yields (>90%) and high purity. Figure 45: Solid state structures of Ru(phenBr) (left) and Ru(phenBr 2 ) (right). Counter ions, coordinated solvents and hydrogen atoms were omitted for clarity. Ellipsoids were drawn at 60% level in this ORTEP representation. For the characterization of the products 1 H- and 13 C-NMR methods were applied. In the case of Ru(phenBr 2 ) nine signals in the aromatic region of the 1 H-NMR spectrum and two signals in the aliphatic region were observed which indicated a dissimilar magnetic environment around the pyridine units of the tbbpy-ligand as expected. In the 13 C-NMR spectrum, all carbon atoms could be assigned according to COSY, HMBC and HSQC methods. Electrospray mass spectrometry (ESI MS) exhibited a molecular ion at m/z = 1121.9 which corresponds to the fragment [M-PF 6 ] + and matches the calculated isotopic pattern of (C 48 H 54 N 6 Br 2 RuPF 6 ). For the compound Ru(phenBr) 13 signals in the aromatic region of the 1 H-NMR spectrum and two signals in the aliphatic region were observed. A singlet at δ = 8.612 ppm for the 6-position and six more aromatic signals were assigned to the phenBr-ligand which indicated a slightly changed magnetic environment of the two phenanthroline halves due to the bromination in |65|
|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| addition to the previously observed shift in the case of the tbbpy-ligand. All 26 carbon atoms could be assigned in the 13 C-NMR spectrum according to a combination of COSY, HMBC and HSQC methods. ESI MS experiments exhibited two prominent peaks at m/z = 1042.1 and 897.2 which correspond to the fragments [M-PF 6 ] + and [M-2PF 6 ] + . Both isotopic patterns matched the calculated patterns for the correct sum formula and thus the desired compounds. The chemical shifts in the NMR spectrum and the observed molecular ions of Ru(phenBr) are very similar to the complex [Ru(tbbpy) 2 (5-chloro-1,10-phenanthroline)] (Ru(phenCl)), peviously prepared by Rau et al. [116] In addition, it was possible to obtain suitable crystals for X-ray diffraction of both compounds by recrystallization from acetone/water and acetonitrile/water respectively as depicted in figure 45. These data support the assignment of a conventional distorted octahedral coordination sphere for both complexes. The detailed discussion of the solid state structure can be found in the combined discussion of all other prepared phenBr-type complexes at the end of this section (page 69 ff.). The synthesis of the higher phenBr 2 -substituted complexes [Ru(tbbpy) 3-n (phenBr 2 ) n ] 2+ (n = 2, 3) required the preparation of the [Ru(̂LL) 2 Cl 2 ]-derivative (Ru(phenBr 2 ) 2 Cl 2 ) as depicted in figure 46. Br Br Br Br Br Br N N + Cl Cl Ru Cl Cl n MW DMF N N N Ru N Cl Cl + N N N Ru N N N Br Br Br Br Br Br Figure 46: Synthesis of the, relating to phenBr-type ligands, homoleptic ruthenium complexes. When these conditions were applied to the related phenBr 4 ligand to prepare the higher substituted complexes [Ru(tbbpy) 3-n (phenBr 4 ) n ] 2+ (n = 2, 3), no product could be isolated. It has been speculated that this finding correlated to the electronic structure of phenBr 4 , i.e. a reduced electron density at the N-donor set of the phenanthroline. [127] The required precursor for this synthesis [Ru(cod)Cl 2 ] n was prepared according to literature |66|
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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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Page 28 and 29: |1.7 Mimicking Photosynthesis| So t
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|3.3 NN-NHC-Ligand bbip: Toward Sec
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|3.4 Outlook, Exploratory Investiga
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|4 Summary| 4 Summary Against the b
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|4 Summary| The resulting complexes
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|4 Summary| 10 [TEA] + TEA visible
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|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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