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|6.1 Synthesis of the Organic Ligands| 6.1.11 Attempted Synthesis of the triethylborane adduct of 1,3-dibenzyl-1H-imidazo[4,5-f][1,10]phenanthroline-2-ylidene - bbipBEt 3 For the synthesis, 0.41 ml of a 1 M solution of HLiB(Et) 3 were added to a stirred solution of 100 mg bbip in 20 ml of dry tetrahydrofuran under argon atmosphere at -80°C. Upon addition a darkening of the solution toward yellow was observed. The temperature was raised to room temperature within 12 hours after the reaction time of 20 minutes at -80°C. After removal of the solvent and dying under high vacuum 1 H-NMR spectra were recorded in dry chloroform-d and dry acetonitrile-d 3 . It was observed that the formed product is not sensitive to air. According to the obtained NMR-spectra it could be concluded that the hydrogenated product was formed. Indicators are signals for the A-, B-, C-protons which refer to the symmetric ligand, a signal which refers to the D-position with an peak area of two protons at 4.7 ppm and the missing characteristic triplet and quartet signals for the ethyl groups at ∼1 ppm. 9 N N 10 11 6 4 5 CH 2 N N CH 2 H H Ar 2 Ar 1 H-NMR (CDCl 3 , 400 MHz): δ = 8.97 (d, 2H (6/9) , 3 J = 3.6Hz), 8.35 (dd, 2H (4/11) , 3 J = 8.3 Hz, 4 J = 1.0 Hz), 7.62 (dd, 2H (5/10) , 3 J = 4.5 Hz, 3 J = 8.3 Hz), 7.31 (m, 10H (Ar)) , 4.76 (s, 2H (2)) , 4.25 (d, 2H (CH2 ), 2 J = 23.7 Hz), 4.19 (d, 2H (CH2 ), 2 J = 26.0 Hz) ppm. 1 H-NMR (CD 3 OD, 400 MHz): δ = 8.91 (dd, 1H (6/9) , 3 J = 4.4Hz, 4 J = 1.6 Hz), 8.36 (dd, 2H (4/11) , 3 J = 8.3 Hz, 4 J = 1.6 Hz), 7.64 (dd, 2H (5/10) , 3 J = 8.3 Hz, 3 J = 4.3 Hz), 7.29 (m, 6H (Ar)) , 7.20 (m, 4H (Ar)) , 4.69 (s, 2H (2)) , 4.13 (s, 4H (CH2 )) ppm. 6.1.12 1-Ethyl-1H-imidazo[4,5-f][1,10]phenanthroline - eip Under argon atmosphere 1.3 g (5.9 mmol) of ip and 260 mg (6.49 mmol) of sodium hydride (60% in paraffin) were suspended in 50 ml of dry DMF as described in method L2. After stirring and sonicating for 30 min the imidazolide anion was completely dissolved and no further gas evolution was observed. Then 440 µl (5.9 mmol) of bromoethane were added and the solution was stirred for three more hours at room temperature. After the reaction time the solvent was removed completely under vacuum and the residue was redissolved in chloroform and washed with water. The combined organic phases were dried over Na 2 SO 4 . After removal of the solvent the crude product was purified by column chromatography using chloroform and silica gel 60 as phase system. Yield: 1.43 g (5.8 mmol, 98%) of a colorless solid. |207|
|6.1 Synthesis of the Organic Ligands| 10 9 N N 6 5 4 11 CH 3 CH 2 N 2 N eip 1 H-NMR (400 MHz, CDCl 3 /DMF): 9.116 (dd, 2H (6/9) , 3 J = 4.2 Hz, 4 J = 1.4 Hz), 8.929 (dd, 1H (4) , 3 J = 8.0 Hz, 4 J = 1.6 Hz), 8.488 (dd, 1H (11) , 3 J = 8.2 Hz, 4 J = 1.4 Hz), 7.959 (s, 1H (2)) , 7.675 (dd, 1H (5) , 3 J = 8.0 Hz, 4 J = 4.4 Hz), 7.649 (dd, 1H (10) , 3 J = 8.0 Hz, 3 J = 4.4 Hz), 4.611 (q, 2H (CH3 ), 3 J = 7.2 Hz), 1.655 (t, 3H (CH2 ), 3 J = 7.2 Hz) ppm. 13 C-NMR (100 MHz, CDCl 3 /DMF): 148.82 (1C (6) ), 147.85 (1C (9 )), 144.76 (1C (7”) ), 144.10 (1C (7’) ), 141.98 (1C (2) ), 137.55 (1C (3’) ), 130.09 (1C (4) ), 128.15 (1C (11) ), 124.29 (1C (1’) ), 123.70 (1C (11”) ), 123.48 (1C (5) ), 122.54 (1C (10) ), 119.75 (1C (3”) ), 42.79 (1C (CH3 )) ppm. Crystals suitable for X-ray diffraction were obtained from hot toluene. Crystal data for eip: C 6 H 12 N 4 , M r = 1.419 g /mol, colorless crystal, size 0.05 × 0.05 × 0.05 mm 3 , triclinic, space group P1 (No. 2), a = 7.9463(5), b = 9.0538(.), c = 17.1468(16) Å, α = 103.419(4), β = 97.861(5), γ = 99.828(5)°, V = 1162.13(17) Å 3 , T = -90(2)°C, Z = 4, ρ calcd. = 1.419 g /cm 3 , µ (Mo-Kα) = 0.89 cm -1 , F(000) = 520, 7840 reflections in h(- 10/9), k(-11/1), l(-22/20) measured in the range 1.24° ≤ Θ ≤ 27.45°, completeness Φ max = 96.2%, 5114 independent reflections, R int = 0.0476, 2556 reflections with F o > 4σ(F o ), 345 parameters, 0 restraints, R obs. = 0.0653, wR 2 obs. = 0.1379, R all = 0.1634, wR 2 all = 0.1718, GOOF = 0.982, largest difference peak and hole: 0.418/-0.278 e /Å 3 . The data file TT3766 includes the complete crystallographic data and can be obtained from Dr. Helmar Görls (IAAC, FSU-Jena). Ellipsoids are drawn at 70% probability in the molecular structure of eip. Selected bond length (Å) and angels (°): 6.1.13 3,3’-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis-(1-ethyl-1Himidazo[4,5-f][1,10]phenanthrolin-3-ium) dibromide - edip According to the general procedure, described in method L3, 200 mg (8005 µmol) of eip and 130 mg (405 µmol) of bisbromethyldurene were dissolved in 50 ml of DMF. The reaction mixture was stirred for 60 h at 80°C. Already after 24 h a bulky was precipitate formed. This precipitate |208|
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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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|3.2 Bisphenanthroline: A Suitable
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f f f f f f |3.2 Bisphenanthroline:
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|3.3 NN-NHC-Ligand bbip: Toward Sec
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Page 168 and 169: |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 217: |6.1 Synthesis of the Organic Ligan
Page 223 and 224: |6.2 Synthesis of the Metal Complex
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
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