Reaction behavior of iron and copper complexes towards dioxygen [Elektronische Ressource] / vorgelegt von Jörg Astner

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• Publié par: justus-liebig-universitat_giessen
• Publié le: 01 janvier 2006
• Nombre de lectures: 9
• Langue: English
• Poids de l'ouvrage: 1 Mo

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JUSTUS-LIEBIG-UNIVERSITÄT GIESSEN
INSTITUT FÜR ANORGANISCHE UND ANALYTISCHE CHEMIE












REACTION BEHAVIOR OF IRON AND COPPER
COMPLEXES TOWARDS DIOXYGEN

Inaugural-Dissertation
zur Erlangung des Doktorgrades
der Naturwissenschaften
im Fachbereich Biologie und Chemie
der Justus-Liebig-Universität Gießen

vorgelegt von

Jörg Astner
aus
Erlangen JUSTUS-LIEBIG-UNIVERSITÄT GIESSEN
INSTITUT FÜR ANORGANISCHE UND ANALYTISCHE CHEMIE












REACTION BEHAVIOR OF IRON AND COPPER
COMPLEXES TOWARDS DIOXYGEN

Inaugural-Dissertation
zur Erlangung des Doktorgrades
der Naturwissenschaften
im Fachbereich Biologie und Chemie
der Justus-Liebig-Universität Gießen

vorgelegt von

Jörg Astner
aus
Erlangen
Acknowledgements
This work was carried out between March 2002 and December 2005 at the
Institute of Inorganic and Analytical Chemistry at the Justus-Liebig-University of
Gießen under the supervision of Prof. Dr. S. Schindler.

I especially want to thank Prof. Dr. S. Schindler for his excellent guidance, the
fruitful scientific discussions and for financial support.

Furthermore I wish to thank my colleagues Dr. M. Schatz, Dr. M. Leibold, Dr. J.
Huber, S. Turba, C. Würtele, T. Neuwert, Dr. Jing-Yuan Xu, T. Nebe, L. Römmling,
J. Müller, F. Mehlich, S. Kisslinger and I. Kerezsi for their interest in my work and
for maintaining a pleasant atmosphere in the group. I want to mention especially
Dr. M. Weitzer; Dr. D. Utz, Dr. S. P. Foxon, and Dr. H. Weiss for their advice and
friendship in the starting phase of my work.

I would like to express my gratitude to Prof. Dr. R. Mukherjee, Dr. J. Mukherjee
and Dr. V. Balamurugan and the whole group of R. Mukherjee for their help and
friendship during my stay at the IIT Kanpur, India.

Last but not least I would like to thank the people of the Institute of Inorganic and
Analytical Chemistry at the Justus-Liebig-University of Gießen and of the Institute
of Inorganic and Analytical Chemistry at the Friedrich-Alexander-University of
Erlangen-Nürnberg for their support of my work.















For my Parents













For Maike


Table of Contents
Acknowledgements ................................................................................................iv
Table of Contents................................................................................................. viii
Ligands used......................................................................................................... xii
Abbreviations........................................................................................................ xiv
Chapter 1 – Introduction......................................................................................... 1
1.1 Motivation ..................................................................................................... 1
1.2 Iron and copper proteins............................................................................... 1
1.3 Mechanisms of dioxygen binding.................................................................. 4
1.4 Characterisation............................................................................................ 5
1.5 Projects......................................................................................................... 6
Chapter 2 - Chelate Ring Size Variations and their Effects on Coordination
Chemistry and Catechol Dioxygenase Reactivity of Iron(III) Complexes................ 7
2.1 Introduction................................................................................................... 7
2.2 Experimental Section.................................................................................... 9
2.2.1 General Remarks.............................................................................. 9
2.2.2 Physical Measurements.................................................................... 9
2.2.3 Stopped-flow Measurements. ........................................................... 9
2.2.4 Determination of the Catechol 1,2-Dioxygenase activity................. 10
2.2.5 Spectrophotometric Titrations. ........................................................ 10
2.2.6 Ligand Syntheses. .......................................................................... 11
2.2.7 Complex Syntheses. ....................................................................... 11
2.2.8 X-ray Crystallographic studies. ....................................................... 12
2.3 Results and Discussion............................................................................... 12
2.4 Comparative Discussion. ............................................................................ 23
2.5 Summary .................................................................................................... 24
viii Table of Contents
Chapter 3 - Iron(III) Complexes with the Ligands N',N'-bis[(2-
pyridyl)methyl]ethylenediamine (uns-penp) and the Amide N-Acetyl-N'N'-bis[(2-
pyridyl)methyl]ethylenediamine (acetyl-uns-penp) ............................................... 25
3.1 Introduction................................................................................................. 25
3.2 Results and Discussion............................................................................... 26
3.2.1 [Fe (acetyl-uns-penp) O](ClO ) x H O (6). .................................... 27 2 2 4 2 2
3.2.2 [Fe(acetyl-uns-penp)(tcc)Br] x (C H ) O (7).................................... 33 2 5 2
3.2.3 [{Fe(acetyl-uns-penp)(tcc)} O] x (C H ) O·CH OH (8). ................... 34 2 2 5 2 3
3.2.4 [Fe(uns-penp)Cl ]ClO x CH CN (9). .............................................. 38 2 4 3
3.2.5 [{Fe(uns-penp)Cl} O](ClO ) x 2CH CN (10)................................... 39 2 4 2 3
3.3 Conclusions ................................................................................................ 40
3.4 Experimental............................................................................................... 41
3.4.1 Materials. ........................................................................................ 41
3.4.2 Physical Measurements.................................................................. 41
3.4.3 Syntheses ....................................................................................... 41
3.4.4 X-ray Crystallographic Studies........................................................ 43
3.4.5 Determination of the Catechol 1,2-Dioxygenase activity................. 44
3.4.6 Spectrophotometric Titrations. ........................................................ 44
Chapter 4 - Reaction behavior of dinuclear copper(I) complexes with m-xylyl-
based ligands towards dioxygen .......................................................................... 45
4.1 Introduction................................................................................................. 45
4.2 Results and Discussion............................................................................... 47
4.3 Phenolate bridged complexes..................................................................... 53
4.4 Magnetic characteristics ............................................................................. 55
4.5 Conclusions ................................................................................................ 57
4.6 Experimental............................................................................................... 58
4.6.1 Reagents and materials .................................................................. 58
ix Table of Contents
4.6.2 Physical measurements.................................................................. 58
4.6.3 Ligand Syntheses ........................................................................... 59
4.6.4 Crystallography............................................................................... 63
Chapter 5 - Copper(I) Complexes with Tridentate Ligands and their Reactivity
towards Dioxygen................................................................................................. 64
5.1 Introduction 64
5.2 Experimental Section.................................................................................. 66
5.2.1 Materials and Reagents. ................................................................. 66
5.2.2 Physical Measurements. 66
5.2.3 Kinetic Measurements. ................................................................... 66
5.2.4 X-ray Crystallography. .................................................................... 67
5.2.5 Syntheses of ligands....................................................................... 68
5.2.6 Synthesis of Copper(II) Complexes. ............................................... 69
5.3 Results and Discussion............................................................................... 71
5.3.1 Syntheses of ligands and co