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f f f f f f |3.2 Bisphenanthroline: A Suitable Molecular Bridge?| 7.0 phenphen Ru(phenphen)Ru Ru(phenphen) * f f f f f f f f Ru(phenphen)Pt * Pt Pt Pt Pt PtPt Pt Pt Pt Pt Pt Pt Pt Pt 9.5 9.0 8.5 8.0 7.5 / ppm Intensity / a.u. N N N N N N Figure 66: Aromatic region of the 1 H-NMR spectra of phenphen and the resulting ruthenium complexes Ru(phenphen)Ru, Ru(phenphen) and Ru(phenphen)Pt in acetonitrile-d 3 . |93|
|3.2 Bisphenanthroline: A Suitable Molecular Bridge?| 3.2.3 Structural Analysis Fortunately, after the synthesis X-ray suitable crystals of phenphen and Ru(phenphen) were obtained from solvent mixtures of water and ethanol (see figure 68). Figure 67: Molecular structure of phenphen (left) and Ru(phenphen) (right). Hydrogen atoms, solvent molecules and anions were omitted for clarity. The torsion angle between the rotational hindered phenanthroline moieties is 65.7(2)° in phenphen and 83.9(3)° in the ruthenium complex respectively. Most prominent is the fact that both crystal structures emphasize the twisted nature of the bridging ligand. The determined torsion angles θ about the C-C-single bonds between the two phenanthroline spheres differ from each other (θ phenphen = 65.7(2)° < θ Ru(phenphen) = 83.9(3)°) but this may be attributed to packing effects according to the low energy barrier for the rotation. The bond length of the bridging C-C-single bond remains unchanged upon complexation (d phenphen (C5-C5’) = 1.489(3) Å in phenphen and d Ru(phenphen) (C5-C17) = 1.500(4) Å in the mononuclear complex) but turns out to be slightly longer than the typical C(sp 2 )-C(sp 2 ) bond length of 1.47 Å, possibly due to the torsion. All Ru-N distances in Ru(phenphen) differ slightly but remain in the range of 2.053 - 2.070 Å, which is expected for ruthenium complexes with bipyridine or phenanthroline-type ligands. [120, 108, 140, 125] Comparison of the different coordination sites exhibits the same values for the bond lengths and angles in phenphen and in the free coordination sphere of Ru(phenphen). The ruthenium containing coordination |94|
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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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|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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