From mechanistic studies on biorelevant Pt(II) complexes to the development of educational concepts [Elektronische Ressource] = Von mechanistischen Untersuchungen an biorelevanten Pt(II)-Komplexen zur Entwicklung alternativer Lehrkonzepte / vorgelegt von Wolfgang Schießl

Wolfgang Schiessl

Informations

• Publié par: friedrich-alexander-universitat_erlangen-nurnberg
• Publié le: 01 janvier 2006
• Nombre de lectures: 53
• Langue: English
• Poids de l'ouvrage: 3 Mo

Extrait

From mechanistic studies on biorelevant Pt(II) complexes to
the development of educational concepts

Von mechanistischen Untersuchungen an biorelevanten
Pt(II)-Komplexen zur Entwicklung alternativer
Lehrkonzepte
Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität
Erlangen-Nürnberg zur Erlangung des Doktorgrades
vorgelegt von
Wolfgang Schießl
aus Amberg
Als Dissertation genehmigt von den naturwissenschaftlichen Fakultäten der
Friedrich-Alexander-Universität Erlangen-Nürnberg.






















Tag der mündlichen Prüfung: 02.05.2006
Vorsitzender der Promotionskomission: Prof. Dr. Donat-Peter Häder
Erstberichterstatter: Prof. Dr. Dr h.c. mult. Rudi van Eldik
Zweitberichterstatter: Prof. Dr. P. Pfeifer
Dedicated to true friendship …

“Friends are the family you choose for yourself.”
Edna Buchanan
Acknowledgements
I wish to thank Prof Dr. Dr. h.c. mult. Rudi van Eldik for the supervision of this
work, his continuous support and trust in me, and for giving me the opportunity to
come up with and fulfill even unusual ideas.
I am grateful towards Prof. Dr. Peter Pfeifer for supporting and guiding my work in
the field of chemical didactics. Our discussions were very encouraging and fruitful.
I would like to thank Dr. Ralph Puchta, room-mate, colleague and “cranky art-
critic” for supporting my advancement by many constructive ideas and discussions.
Many thanks to all the members of the group. In these last years, our friendship
soon grew far beyond working colleagues.
Special thanks to Hakan Ertürk and Hakos Tria. I will live out the prophet’s answer.
Thanks to all my friends. To be able to rely on all of you anytime is a great gift.
Finally I would like to thank my family – my mom and dad, and my brother Michael.
I greatly appreciate your consistent support in every part of my life. I owe you so
much.






Die vorliegende Arbeit entstand in der Zeit von August 2001 bis Februar 2006 am
Institut für Anorganische und Analytische Chemie der Friedrich-Alexander-
Universtität Erlangen-Nürnberg.

Publications and Conference Contributions
Publications
1. Wolfgang Schiessl, Andreas Hofmann, Carlos Dücker-Benfer, Nadine Summa,
Michael Galle and Rudi van Eldik, “Magic Show 2003: Im Auftrag der
Chemie unterwegs”, GIT Labor Fachz. 2003, 47, (6), 614-616.
2. Wolfgang Schiessl, Nadine Summa, Christian Weber, Sonja Gubo, Carlos
Dücker-Benfer, Ralph Puchta, Nico van Eikema-Hommes, and Rudi van
Eldik, “Experimental and theoretical approaches to the protonation of
thiourea: a convenient nucleophile in coordination chemistry revisited”, Z.
Anorg. Allg. Chem. 2005, 631, (13-14), 2812-2819.
3. Wolfgang Schiessl, Ariane Brausam, “Leuchtender Tee”, NiU Chemie 2005,
16, (4-5), 91
4. Carlos Dücker-Benfer, Wolfgang Schiessl, Michael Galle and Rudi van Eldik,
“Alles wird gut – Der neue Sicherheitsfilm für das Arbeiten in chemischen
Laboratorien”, GIT Labor Fachz. 2005, 49, (11), 964.
5. Nadine Summa, Wolfgang Schiessl, Ralph Puchta, Nico van Eikema-Hommes
and Rudi van Eldik, “Thermodynamic and Kinetic Studies on Reactions of
Pt(II) Complexes with Biologically Relevant Nucleophiles”, Inorg. Chem.
2006, 45, (7), 2948-2959.
6. Wolfgang Schiessl, Carlos Dücker-Benfer, Nadine Summa, Ariane Brausam,
Peter Pfeifer and Rudi van Eldik, “Chemie Edutainment – Zaubervorlesung
mit Salvador Dalí”, Chemie in unserer Zeit 2006, 40, accepted for
publication in issue 3/2006.

7. Wolfgang Schiessl, Peter Pfeifer and Rudi van Eldik, “Chemie Edutainment
auf dem Prüfstand: Evaluierung der Zaubervorlesung mit Salvador Dalí”,
ChemKon, submitted.
8. Wolfgang Schiessl, Ralph Puchta, Živadin D. Bugarčić, Frank Heinemann and
Rudi van Eldik, “Systematic counter-ion tuning of the solid state structure of
2+[Pt(thiourea)4] ”, Inorg. Chem., submitted.

Conference contributions: Posters
1. “Controlling the Reactivity of 'L3'PtII(H O) Complexes : A systematic π-2
Acceptor Study”, Chemistry Symposium Rennes–Erlangen, Apr. 18 – 20
2001, Rennes, France.
2. “Electronic tuning of the reactivity of bifunctional Pt(II) complexes”,
Workshop in Biophysical and Bioinorganic Chemistry, Sep. 08 – 17 2001,
Louvain-la Neuve, Belgium.
3. “Tuning the reactivity of Pt(II)Complexes: π-acceptor effects in cis-platin
related complexes”, Inorganic Reaction Mechanism Meeting, Jan. 08 – 10
2004, Athens, Greece.

Abbreviations
Ligands
A N-donating ligand
Am N-donating bidentate amine ligands like en, dach, amp, bpy
AMD473 cis-Amminedichloro(2-methylpyridine) platinum(II)
amp aminomethylpyridine
-BPh tetraphenyl-borate anion
bpy 2,2’-bipyridine
dach diaminocyclohexane
en ethylenediamine
Complexes
2+ Pt(amp) [Pt(aminomethylpyridine)(H O) ]2 2
2+Pt(bpy) [Pt(N,N’-bipyridine)(H O) ] 2 2
2+ Pt(dach) [Pt(diaminocyclohexane)(H O) ]2 2
2+Pt(en) [Pt(ethylenediamine)(H O) ] 2 2
Oxaliplatin (trans-1,2-diaminocyclohexane)oxalatoplatinum(II)
Other Chemicals
DMSO dimethylsulfoxide
HOTf trifluoromethanesulfonic acid
-5’GMP guanosine-5’-monophosphate
L-Met L-methionine
MeOH methanol
-OTf trifluoromethanesulfonate, CF SO 3 3
TMS tetramethylsilane
TSP trimethylsilylpropionic acid

Other Abbreviations
DFT density functional theory
DNA deoxyribonucleic acid
ε dielectric constant
-34h Planck constant, 6.6261 x 10 J s
-23kb Boltzmann constant, 1.3807 x 10 J/K
k observed rate constant for pseudo-first-order reactions obs
k ,k rate constants 1 2
NMR nuclear magnetic resonance
-1 -1R gas constant, 8.3145 J K mol
T temperature
ts transition state
TU thiourea
X leaving group
Z counter anion
#ΔH activation enthalpy
#ΔS activation entropy
#ΔV activation volume

Table of Contents
1. Introduction.......................................................................................................13
2. Experimental and Theoretical Approaches to the Protonation of
Thiourea: A Convenient Nucleophile in Coordination Chemistry
Revisited ............................................................................................................21
2.1. General remark.............................................................................................21
2.2. Abstract.........................................................................................................21
2.3. Introduction................................................................................................. 22
2.4. Experimental section................................................................................... 26
2.4.1. Chemicals ............................................................................................... 26
2.4.2. Instrumentation and measurements..................................................... 26
2.4.3. Computations ......................................................................................... 27
2.5. Results and Discussion................................................................................28
2.5.1. Spectrophotometric pH titrations .........................................................28
2.5.2. NMR and Mass spectra .......................................................................... 33
2.5.3. Theoretical Calculations......................................................................... 35
2.6. Conclusions.................................................................................................. 39
2.7. References.....................................................................................................41
2.8. Supporting information .............................................................................. 45
3. Thermodynamic and kinetic studies on reactions of Pt(II) complexes
with biologically relevant nucleophiles............................................................ 49
3.1. General remark............................................................................................ 49
3.2. Abstract........................................................................................................ 49
3.3. Introduction.................................................................................................50
3.4. Experimental Section .................................................................................. 53
3.4.1. Chemicals and ligands ........................................................................... 53
3.4.2. Synthesis of complexes .......................................................................... 53
3.4.3. Instrumentation and Measurements..................................................... 55
3.4.3.1. NMR Spectroscopy and Elemental Analysis ................................. 55
9
3.4.3.2. Spectrophotometric pH-Titrations ................................................ 55
3.4.3.3. UV-Vis kinetic ex