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Informations
Publié par | ludwig-maximilians-universitat_munchen |
Publié le | 01 janvier 2011 |
Nombre de lectures | 31 |
Langue | Deutsch |
Poids de l'ouvrage | 27 Mo |
Extrait
Dissertation zur Erlangung des Doktorgrades
der Fakultät für Chemie und Pharmazie
der Ludwig-Maximilians-Universität München
Carbohydrate-Metal Chemistry:
Complexes of Palladium(II) and their Characterization via
NMR Spectroscopy and X-Ray Crystallography
Thorsten Bastian Allscher
aus
Altötting am Inn
2011
Erklärung
Diese Dissertation wurde im Sinne von § 13 Abs. 3 der Promotionsordnung vom 29. Januar
1998 (in der Fassung der sechsten Änderungssatzung vom 16. August 2010) von Herrn Prof.
Dr. Peter Klüfers betreut.
Ehrenwörtliche Versicherung
Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet.
München, den 04. Juli 2011
Thorsten Allscher
Dissertation eingereicht am: 04. Juli 2011
1. Gutachter: Prof. Dr. Peter Klüfers
2. Gutachter: Prof. Dr. Konstantin Karaghiosoff
Mündliche Prüfung am: 02. August 2011
Diese Arbeit wurde in der Zeit von Oktober 2006 bis Juli 2011 am Department für Chemie
und Pharmazie der Ludwig-Maximilians-Universität München am Lehrstuhl für
Bioanorganische Chemie und Koordinationschemie unter Anleitung von Herrn Prof. Dr. Peter
Klüfers durchgeführt.
Meinen Eltern
Contents
1 Introduction .......................................................................................................................................... 1
1.1 The biological importance of carbohydrates ................. 1
1.2 Industrial applications of carbohydrates ....................................................................................... 2
1.3 Carbohydrate structure and conformation ..................... 8
1.4 NMR spectroscopy and the Karplus equation ............................................................................. 14
1.5 Aims of this work ........................................................ 17
2 Results ................................................................................................................ 19
2.1 Palladium(II) fragments: nomenclature and characteristics ........................ 19
2.1.1 [Pd(dmen)(OH) ] and [Pd(tmen)(OH) ] .............................................................................. 20 2 2
2.1.2 [Pd(tmchxn)(OH) ] .............................................. 21 2
2.1.3 [Pd(teen)(OH) ] ................................................................................... 23 2
2.1.4 [Pd(tn)(OH) ] ....................................................... 24 2
2.1.5 [Pd(bpy)(OH) ] and [Pd(phen)(OH) ] ................................................................................. 24 2 2
2.2 Simple diols: ethane-1,2-diol and anhydroerythritol complexes with Pd-phen .......................... 26
2.3 The polyols: open-chain carbohydrate complexes of palladium(II) ........................................... 28
2.3.1 The tetritols: erythritol and D-threitol .................................................. 30
2.3.2 The pentitols: ribitol and xylitol .......................................................... 33
2.3.3 The hexitols ......................................................................................... 33
2.4 Palladium(II)–polyol complexes in neutral aqueous solution ..................................................... 47
2.4.1 μ-Triolato-chelation and ligand conformation at pH 8–9 .................... 48
2.4.2 Pd (μ-OH) -derived threo-tetraolato bridging at pH 7–8 ................................ 54 4 4
2.4.3 Pd (μ-OH) -derived triolato bridging at pH 7–8 .................................................................. 62 3 3
2.5 Dihydroxymalonic acid – complexes of palladium(II) with ketone hydrates ............................. 65
2.6 The inositols: from polyols to pyranose rings ............................................................................. 66
2.7 Conformational fluctuation in palladium(II)–methyl aldopentopyranoside complexes ............. 74
i
2.8 Metalation-induced conformational fluctuation of palladium(II)–aldopentose complexes ........ 84
2.8.1 D-Arabinose ......................................................................................................................... 85
2.8.2 D-Ribose .............................. 91
2.8.3 D-Lyxose ................................................................................................ 95
2.8.4 D-Xylose ............................ 101
2.9 Coordination-induced shift patterns of palladium(II)–methyl hex(ul)oside complexes ........... 105
2.9.1 The methyl hexopyranosides of D-galactose, D-glucose and D-mannose .......................... 105
2.9.2 The methyl fructosides ...................................................................................................... 113
2.10 Palladium(II) chelation with Pd-tmen by the common hexoses ............. 118
2.10.1 D-Galactose ...................................................................................................................... 119
2.10.2 D-Glucose ......................... 121
2.10.3 D-Mannose ....................................................................................................................... 123
2.11 The difficult determination of the palladium(II)–hexulose complexes ................................... 126
2.11.1 D-Fructose ........................................................................................................................ 127
2.11.2 D-Tagatose ....................... 130
2.11.3 L-Sorbose ......................................................................................................................... 133
2.11.4 D-Psicose .......................... 135
2.12 The dialdoses: A first investigation......................................................................................... 137
2.12.1 erythro-Tetrodialdose ...................................... 138
2.12.2 xylo-Pentodialdose ........................................................................... 139
2.12.3 galacto-Hexodialdose ...................................... 142
2.12.4 D-manno-Hexodialdose ................................................................... 145
2.13 The fructose-containing di- and trisaccharides ....................................... 149
2.13.1 D-Sucrose ......................................................................................................................... 150
2.13.2 D-Turanose ....................... 152
2.13.3 D-Maltulose ...................................................................................................................... 153
2.13.4 D-Lactulose 154
2.13.5 D-Leucrose ....................................................................................................................... 155
2.13.6 D-Palatinose ..................... 157
2.13.7 D-Melecitose .................................................................................................................... 158
ii
2.13.8 D-Raffinose ...................................................................................................................... 159
2.14 From disaccharides to the polysaccharides with β-connected units ........................................ 161
2.14.1 D-Lactose ......................................................................................................................... 161
2.14.2 D-Cellobiose and Cellulose .............................. 163
2.15 From disaccharides to the oligosaccharides with α-connected units....................................... 166
2.15.1 α,α-D-Trehalose ............................................................................... 168
2.15.2 D-Melibiose ...................................................... 169
2.15.3 D-Maltose ......................................................................................... 171
2.15.4 D-Maltotriose ................................................... 173
2.15.5 D-Maltoheptaose and amylose ......................................................... 178
2.16 The cyclodextrins .................................................................................... 181
3 Discussion ........................................................................ 185
II3.1 The Pd N fragments: characteristics and differences .............................. 185 2
II3.2 The Pd N fragments‘ influence on the hydrogen-bonding network ........................................ 186 2
3.3 Conformational fluctuation in palladium(II)–methyl aldopentopyranoside and aldopentose
complexes ....................................................................................................... 188
3.4 Metalation of the methyl hex(ul)osides ..................................................................................... 190
3.5 Metalation of the hexoses ..........................