Cyclen transition metal complexes as biomimetic catalysts, phosphate anion sensors and building-blocks in supramolecular assemblies [Elektronische Ressource] / vorgelegt von Kristina Michaela Woinaroschy
179 Pages
English
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Cyclen transition metal complexes as biomimetic catalysts, phosphate anion sensors and building-blocks in supramolecular assemblies [Elektronische Ressource] / vorgelegt von Kristina Michaela Woinaroschy

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179 Pages
English

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Cyclen Transition Metal Complexes as Biomimetic Catalysts, Phosphate Anion Sensors and Building-blocks in Supramolecular Assemblies Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) der naturwissenschaftlichen Fakultät IV – Chemie und Pharmazie – der Universität Regensburg vorgelegt von Kristina Michaela Woinaroschy aus Bukarest (Rumänien) 2007 The experimental part of this work was carried out between October 2003 and September 2007 at the Institute of Organic Chemistry at the University of Regensburg, under the supervision of Prof. Dr. B. König. The PhD thesis was submitted on: 06. November 2007 The colloqium took place on: 27. November 2007 Board of examiners: Prof. Dr. J. Heilmann (Chairman) Prof. Dr. B. König (1st Referee) Prof. Dr. R. Gschwind (2nd Referee) Prof. Dr. S. Elz (Examiner) To Alex and my family Acknowledgements I would like to express my sincere gratitude to Prof. Dr. B. König for his continued guidance, encouragement and advice throughout this work.

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Published 01 January 2009
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Cyclen Transition Metal Complexes as
Biomimetic Catalysts, Phosphate
Anion Sensors and Building-blocks in
Supramolecular Assemblies


Dissertation
zur Erlangung des Doktorgrades der Naturwissenschaften
(Dr. rer. nat.)
der naturwissenschaftlichen Fakultät IV
– Chemie und Pharmazie –
der Universität Regensburg




vorgelegt von
Kristina Michaela Woinaroschy
aus Bukarest (Rumänien)
2007






























The experimental part of this work was carried out between October 2003 and September
2007 at the Institute of Organic Chemistry at the University of Regensburg, under the
supervision of Prof. Dr. B. König.















The PhD thesis was submitted on: 06. November 2007
The colloqium took place on: 27. November 2007

Board of examiners: Prof. Dr. J. Heilmann (Chairman)
Prof. Dr. B. König (1st Referee)
Prof. Dr. R. Gschwind (2nd Referee)
Prof. Dr. S. Elz (Examiner)














































To Alex
and my family
Acknowledgements

I would like to express my sincere gratitude to Prof. Dr. B. König for his continued guidance,
encouragement and advice throughout this work.

I would also like to thank the German Environmental Foundation (Deutsche Bundesstiftung
Umwelt, DBU) for awarding me a PhD scholarship and offering me the occasion to make
interesting contacts and learn about new valuable scientific projects during the yearly
seminars and conferences. My special thanks to Dr. J. Lay and Nicole Redeker-Freyer for
their support and valuable friendship.

Thanks are extended to the scientific staff members of the analytical department of the
Faculty of Chemistry and Pharmacy at the University of Regensburg for the quick and precise
measurements, and especially for their constant help when puzzling questions and problems
troubled me. Special thanks to Dr. T. Burgemeister, Mr. F. Kastner, Ms. N. Pustet, Ms. A.
Schramm and Ms. G. Stühler (NMR), Dr. K. K. Mayer, Mr. J. Kiermaier and Mr. W. Söllner
(MS), Mr. H. Schüller (elemental analysis), Dr. M. Zabel and Ms. S. Stempfhuber (X-ray
crystallography) and Mrs. H. Leffler-Schuster, M rs. Britta Badziura and Mrs. Regina
Hoheisel (potentiometric titrations). I thank also the scientific teams of Prof. Dr. O. Reiser
and Prof. Dr. A. Buschauer for the use of the IR spectrometers and high temperature melting
point apparatus. A special thanks to Prof. Dr. R. Winter from the Institute of Inorganic
Chemistry at the University of Regensburg and Dr. Biprajit Sarkar from the University of
Stuttgart for measurements of EPR spectra and the helpful discussions.

I would like to thank Michael Subat for the good collaboration on two of the projects, for
giving me advice and for the long and interesting discussions, whether scientific or personal.
Thanks go also to the two undergraduate students, Stefan Anthofer and Andrei Ursu, for the
good cooperation and their industrious work in the lab. A special thanks to Dr. W. Braig, Dr.
C. Braig, Mrs. E. Liebl, Ms. S. Graetz, Dr. R. Vasold and Mrs. S. Strauss for their support.

I would like to thank all my colleagues, past and present, for making the working environment
positive, constructive, as well as relaxed. My special thanks go to:
Dr. C. Bonauer, Dr. C. Mandl and Dr. T. Graf for making me feel welcome and putting me at
ease at my arrival in the working group. My lab colleagues Dr. Stefan Ritter, Andreas Grauer and Alexander Riechers for making sure the days in the lab are lively and never boring or
ordinary, for the discussions and great laughs. Andrea Späth for having always a cheer-up line
and an open ear for discussion. Jiri Svoboda for the nice evenings playing board games and
the great Czech meals. Robert Knappe for being always himself and for his sincerity.
Giovanni Imperato for all the crazy stuff, for showing me to take things easier and the
delicious food. Britta Badziura, Regina Hoheisel, Simone Strauss and Eisabeth Liebl for all
the nice lunchtimes spent in the kitchen together.

My personal thanks goes to my school friends Alexandra Beca and Catalina Anitei and to
Valentin Lupu for their friendship, all the nice moments spent on the holidays back home, the
many laughs and the constant encouragements.

I would also like to thank the members of the theatre group “Babylon” in the years 2003-2006
for their friendship, for helping me adapt quicker to my new environment, for offering me
unforgettable moments and interesting views on other cultures. Special thanks to Caren,
Christine and Andi for keeping the group together, to Leo, Nazish, Moni, Lissy, Magda,
Gokce, Bille, Pasquale for laughing with tears and to Witalij and Dragisa for sharing with me
the Slavonic spirit.

My most special and biggest thanks go to my husband Alex and to my family (my parents,
grandparents and aunt). A very big “Thank you” from all my heart for giving me all your love
and trust, for never letting me down and giving me always 100% backup. I could not be where
I am today and be the person that I am today without you.












One never notices what has been done;
one can only see what remains to be done.
Marie Curie Table of Contents

A Introduction .............................................................................................................1

B Main Part.................5
1. 1,4,7,10 – Tetraazacyclododecane Metal Complexes as Potent Promoters of
Carboxyester Hydrolysis under Physiological Conditions..........................................5
1.1. Introduction ...........................................................................6
1.2. Results and discussion...........................................................................................8
1.2.1. Syntheses of the ligands L1-L8 and their metal complexes…………….....8
1.2.2. Deprotonation constants (pK ) of the metal-bound H O…....................... 12 a 2
1.2.3. X-ray Crystal Structure of [Zn L2]µ-OH(ClO ) · CH CN · H O……….17 2 4 3 3 2
1.2.4. Hydrolysis of 4-nitrophenyl acetate (NA) promoted by the mononuclear metal
complexes…………………………………………………………………………….....19
1.2.5. Hydrolysis of 4 -nitrophenyl acetate (NA) promoted by the dinuclear metal
complexes Zn L2, Zn L4 and Zn L5……………………………………………………24 2 2 2
1.2.6. Hydrolysis of 4 -
complexes Cu L2, Ni L2, Zn L6 and Zn L7……………………………………………27 2 2 2 2
1.3. Conclusion……………………………………………………………………….33
1.4. Experimental section…………………………………………………………….35
1.5. References……………………………………………………………………….77

2. 1,4,7,10 – Tetraazacyclododecane Metal Complexes as Potent Promoters of
Phosphodiester Hydrolysis under Physiological Conditions………………………..81
2.1. Introduction……………………………………………………………………...81
2.2. Experimental section..………………………………………………………….. 83
2.3. Results and discussion………………………………………..………………... 84
2.4. Conclusion………….....99
2.5. Supporting Information…………………………………………………………100
2.6. References………………………………………………………………………102

3. Phosphate Anion Binding of Dinuclear Zinc-1,4,7,10 – tetraazacyclododecane
Complexes at Physiological Conditions…………………………………………..….107
3.1. Introduction……………………………………………………………………107
3.2. Results and discussion…………………………………………………………111 3.3. Conclusion……………………………………………………………………..126
3.4. Experimental section…………………………………………………………..127
3.5. Supporting Information………………………………………………………..132
3.6. References……………………………………………………………………..142

4. Synthesis and characterization of 1-(2H-Tetrazol-5-yl)-1,4,7,10-tetraaza-
cyclododecane and its Zn(II), Ni(II) and Cu(II) complexes………………………..145
4.1. Introduction…………………………………………………………………….145
4.2. Results and discussion……………………………………………………….....146
4.2.1. Syntheses of the macrocyclic tetraazole ligand and its metal complexes ZnL,
CuL and NiL……………………………………………………………………………146
4.2.2. X-ray Crystal Structure of the dimer [Ni LH ) (H O) ](ClO ) ………..148 2( -1 2 2 2 4 2
4.2.3. Deprotonation Constants (pK ) of the metal complexes…………………150 a
4.3. Experimental section………………………………………………………...... 153
4.4. References………………………………………………………………….......161

C Summary………………………………………………………………………….165

D Appendix………………………………………………………………………….166
Publication list……..……………………………………………………………166
Curriculum Vitae………………………………………………………………..167



















Abbreviations

Bis/Tris Bis[2-hydroxyethyl]-imino-Tris-[hydroxymethyl]-methane
BNPP bis(4-nitrophenyl)phosphate
Boc tert-butoxycarbonyl
BrCN cyanogen bromide
C Celsius
c concentration
calcd. Calculated
CDCl deuterated chloroform 3
CH CN acetonitrile 3
CHES N-cyclohexyl-2-aminoethanesulfonic acid
CI chemical ionisation
ClO perchlorate (anion) 4
DCM dichloromethane
DMSO dimethylsulfoxide
EI electron impact (MS)
EPR electron paramagnetic resonance (spectra)
eq. equivalent
ES electron spray (MS)
Et NH diethylamine 2
Et O diethyl ether 2
EtOAc ethyl acetate
EtOH ethanol
FAB fast atom bombardment
h hours
HCl hydrochloric acid
HClO perchloric acid 4
HEPES N-2-Hydroxyethylpiperazin-N’-2-ethansulfonic acid
HPLC high pressure liquid chromatography
HRMS high resolution mass spectrum
I ionic strength
IR infra red (spectrum)
ITC isothermal titration calorimetry