Chiral oxazoline and bis(oxazoline) ligands [Elektronische Ressource] : new biomimetic models for iron containing nonheme proteins and their application in catalysis / vorgelegt von Caroline Anja Schall

Caroline A. Schall

Sujets

• Gesundheit

Informations

• Publié par: universitat_regensburg
• Publié le: 01 janvier 2008
• Nombre de lectures: 44
• Langue: Deutsch
• Poids de l'ouvrage: 5 Mo

Extrait

CHIRAL OXAZOLINE AND BIS(OXAZOLINE)
LIGANDS – NEW BIOMIMETIC MODELS FOR
IRON CONTAINING NONHEME PROTEINS AND
THEIR APPLICATION IN CATALYSIS

Dissertation


zur Erlangung des Doktorgrades der Naturwissenschaften
Dr. rer. nat.

an der Fakultät für Chemie und Pharmazie
der Universität Regensburg




vorgelegt von

Caroline Anja Schall
aus
Schwandorf


Regensburg 2007




















Die Arbeit wurde angeleitet von: Prof. Dr. O. Reiser


Promotionsgesuch eingereicht am: 05. November 2007


Promotionskolloquium am: 30. November 2007



Prüfungsausschuss: Vorsitz: Prof. Dr. J. Heilmann
1. Gutachter: Prof. Dr. O. Reiser
2. Gutachter: Prof. Dr. R. Gschwind
3. Prüfer: Prof. Dr. R. Winter

2 Der experimentelle Teil der vorliegenden Arbeit wurde unter der Leitung von Herrn Prof. Dr.
Oliver Reiser in der Zeit von August 2004 bis September 2007 am Institut für Organische
Chemie der Universität Regensburg sowie in der Arbeitsgruppe von Prof. Dr. A. Borovik,
University of Kansas, angefertigt.








































Herrn Prof. Dr. Oliver Reiser möchte ich für die Überlassung des äußerst interessanten
Themas, die fortwährenden Diskussionen und seine Unterstützung während der Durchführung
dieser Arbeit danken.

3
4

















for my family…























“Raise new questions,

explore new possibilities,
regard old problems from a new angle.”




Albert Einstein


5 Table of Content
Table of Content
TABLE OF CONTENT ............................................................................................... 6
A. INTRODUCTION ................................................................................................... 8
A.1 Do we need biomimetic models? ....................................................................................................... 8
A.2 Models for nonheme iron enzymes ................................................................................................. 16
A.3 Aim of this work............................................................................................................................... 20
B. MAIN PART – SYNTHESIS................................................................................. 23
B.1 Ligand Synthesis .............................................................................................................................. 23
B.1.1 General Retrosynthesis of Oxazoline, Bis(oxazoline) Ligands and their Derivatives 23
B.1.2 Route to Oxazoline Ligands and their Derivatives 24
B.1.3 Route to Bis(oxazoline) Ligands 28
C. MAIN PART – OXAZOLINE COMPLEX ANALYSIS........................................... 37
C.1 Determination of Stoichiometry and Equilibrium Constant........................................................ 37
C.1.1 Siderophores – A General Introduction 37
C.1.2 Stoichiometry Determination by Job`s Plot Analysis 40
C.1.3 Determination of Equilibrium-Constants 42
C.2 Characterization of Oxazoline-Metal-Complexes ......................................................................... 47
C.2.1 Formation of Iron(III) Complexes using Fe(ClO ) •6(H O) 47 4 2 2
III
C.2.2 Solid-State-Analysis of Iron(III) Complexes – [Fe (7a-9) ]•(ClO ) 48 2 4
III
C.2.3 Liquid-State-Analysis of Iron(III) Complexes – [Fe (7a-9) ]•(ClO ) 50 2 4
C.2.4 Formation of Iron(III) Complexes using Fe(OAc) 55 2
III
C.2.5 Solid-State-Analysis of Iron(III) Complexes – [Fe (7a-9) (OAc)] 56 2
IIIC.2.6 Liquid-State-Analysis of Iron(III) Complexes – [Fe (7a-9) (OAc)] 63 2
C.2.7 Formation of Iron(III) Complexes using Fe(acac) 66 3
III
C.2.8 Liquid-State-Analysis of Iron(III) Complexes – [Fe (7a-9) (acac)] 67 2
C.2.9 Formation of Ruthenium(III) Complexes using [RuCl (benzene)] 70 2 2
IIIC.2.10 Liquid-State-Analysis of Ruthenium(III) Complexes – [Ru (7a-9) ] 71 3
C.2.11 Formation of Zinc(II) Complexes using Zn(ClO ) •6H O 74 4 2 2
IIC.2.12 Solid-State-Analysis of Zinc(II) Complexes – [Zn (7a/9) ] •(ClO ) 75 2 2 4 2
II
C.2.13 Liquid-State-Analysis of Zinc(II) Complexes – [Zn (7a-9) ] •(ClO ) 81 2 2 4 2
28
C.2.14 Formation of a Manganese(III) Complex using Mn(ClO ) •6H O 83 4 2 2
III
C.2.15 Solid-State-Analysis of a Manganese(III) Complex – [Mn (7a) (THF) ]•(ClO ) 83 2 2 4
IIIC.2.16 Liquid-State-Analysis of a Manganese(III) Complex – [Mn (7a) (THF) ]•(ClO ) 87 2 2 4
C.2.17 Summary 89
D. MAIN PART – BIS(OXAZOLINE) COMPLEX ANALYSIS .................................. 90
D.1 Characterization of Bis(oxazoline)-Metal-Complexes .................................................................. 90
D.1.1 Formation of Iron(III) Complexes using Fe(ClO ) •6(H O) 90 4 2 2
IIID.1.2 Solid-State-Analysis of Iron(III) Complexes – Fe ((meso)-4) (H O)]•(ClO ) 92 ox 2 4
III III
D.1.3 Liquid-State-Analysis of Iron(III) Complexes – [Fe (1/2)(H O) ]•(ClO ) and [Fe ((±)-4/(meso)-2 2 4 2
4/5) (H O)]•(ClO ) 95 ox 2 4
D.1.4 Formation of Ruthenium(II) and Ruthenium(III) Complexes using [RuCl (benzene)] 97 2 2
IIID.1.5 Liquid-State-Analysis of Ruthenium(II) and Ruthenium(III) Complexes – [Ru (1/2)(Cl)(solvent)]
II
and [Ru ((±)-4/(meso)-4/5)(Cl) ] 100 2
D.1.6 Formation of Zinc(II) Complexes using Zn(ClO ) •6H O 103 4 2 2

6 Table of Content
II IID.1.7 Solid-State-Analysis of Zinc(II) Complexes – [Zn (1/2)]•(ClO ) and [Zn ((S,S)-4/5)]•(ClO ) 104 4 2 4 2
II II
D.1.8 Liquid-State-Analysis of Zinc(II) Complexes – [Zn (1/2)]•(ClO ) and [Zn ((±)-4/(meso)-4 2
4/5)]•(ClO ) 107 4 2
D.1.9 Summary 110
E. MAIN PART – CATALYSIS............................................................................... 111
E.1 Catalysis.......................................................................................................................................... 111
E.1.1 Functionalization of Alkanes by C-H Bond Activation 111
E.1.2 Oxidation of Ethylbenzene by Oxazoline / Bis(oxazoline) Complexes 114
E.1.3 Preparation of Optical Active Sulfoxides 119
E.1.4 Asymmetric Sulfide Oxidation 120
F. EXPERIMENTAL PART..................................................................................... 123
F.1 General............................................................................................................................................ 123
F.2 Abbreviations ................................................................................................................................. 125
F.3 Oxazoline and Thiazoline Ligands ............................................................................................... 126
F.5 Bis(oxazoline) ligands .................................................................................................................... 134
F.5 Precursor for Oxazoline and Bis(oxazoline) Ligands ................................................................. 142
F.6 General precursor.......................................................................................................................... 154
F.7 Synthesized Complexes of Oxazoline Ligands............................................................................. 159
F.7.1 Iron Complexes 159
F.7.2 Ruthenium Complexes 168
F.7.3 Zinc Complexes 171
F.7.4 Manganese Complex 174
F.8 Synthesized Complexes of Bis(oxazoline) Ligands ...................................................................... 175
F.8.1 Iron Complexes 175
F.8.2 Ruthenium Complexes 179
F.8.3 Zinc Complexes 183
F.9 UV/Vis-Titrations........................................................................................................................... 187
F.9.1 UV/Vis-Job`s Plot Titration 187
F.9.2 UV/Vis-Equilibrium Constant Titration 188
F.9.2 General UV/Vis- and CD-Measurements 190
F.10 Catalysis Reactions ........................................................................................................................ 193
F.10.1 Oxidation of ethylbenzene 193
F.10.2 Oxidation of methyl phenyl sulfide 194
F.11 X-Ray Structure Data.................................................................................................................... 195
G. REFERENCES .................................................................................................. 223
H. CURRICULUM VITAE ....................................................................................... 228
I. ACKNOWLEDGEMENT...................................................................................... 231


7 Introduction
A. Introductio