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Kinetic, Mechanistic and Structural Studies on
in Ionic Liquids

Kinetische, mechanistische und strukturelle Untersuchungen von
in ionischen Flüssigkeiten

Der Naturwissenschaftlichen Fakultät
der Friedrich-Alexander-Universität Erlangen-Nürnberg
Erlangung des Doktorgrades Dr. rer. nat.

vorgelegt von
Matthias Schmeißer
aus ErlangenAls Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der
Universität Erlangen-Nürnberg

Tag der mündlichen Prüfung: 14. September 2011
Vorsitzender der Promotionskommission: Prof. Dr. Rainer Fink
Erstberichterstatter: Prof. Dr. Dr. h. c. mult. Rudi van Eldik
Zweitberichterstatterin: Prof. Dr. Ivana Ivanović-Burmazović


Denn das Törichte an Gott ist weiser als die Menschen und das
Schwache an Gott ist stärker als die Menschen.
Wer sich also rühmen will, der rühme sich des Herrn; so heißt es
schon in der Schrift.

1. Korinther 1, 25 + 31

3 Die vorliegende Arbeit entstand in der Zeit von Februar 2008 bis Mai 2011 am Department
Chemie und Pharmazie der Friedrich-Alexander-Universität Erlangen-Nürnberg.


Meiner Familie

6 Acknowledgements

I would like to thank Prof. Dr. Dr. h. c. mult. Rudi van Eldik for the supervision of my work. I
am particularly grateful for our fruitful discussions, his support, encouragement and
confidence during my scientific development. I appreciate very much the good working
conditions and the opportunity to present our accomplishments internationally.

Many thanks to Dr. Ralph Puchta and Dr. Achim Zahl; Ralph, for his support, our
encouraging discussions and the DFT calculations presented in this thesis; Achim, for the
performance of an enormous amount of NMR measurements. Both of them always were
reliable and helpful persons, whenever needed. Thank you.

I would also like to thank Prof. Dr. Thomas M. Klapötke, Prof. Dr. Axel König, Dr. Jörg
Stierstorfer and Philipp Keil for the efficient collaboration concerning the ionic liquid
[emim][ClO ]. 4

A special “Thank you” to Dr. Peter Illner and his wife Julia, for their constant support and
friendship; Peter, thank you for all the inspiring and amusing conversations during our coffee

Furthermore, I would like to thank all the group members for their support and the good
working atmosphere; I specially acknowledge Svetlana Begel, Dr. Ariane Brausam, Dr.
Carlos Dücker-Benfer, Stephanie Hochreuther, Christoph Fertinger, Simon Kern, Ursula
Niegratschka, Sabine Rotbart, Lars Rower and Raquel Urpi Bertran.

I am also very grateful towards Erna Pösl for all her encouragement and being a “true friend”.

I am highly indebted to my family, especially my parents Gerhard and Isolde Schmeißer for
all their support and encouragement during all these years.

7 Publications and Conference Contributions


• Matthias Schmeisser and Rudi van Eldik, Thermodynamic and Kinetik Studies on
IIIReactions of Fe (meso-[tetra(sulfonatomsityl)porphin]) with NO in an Ionic Liquid.
Trace Impurities Can Change the Mechanism!, Inorg. Chem., 2009, 48, 7466-7475.

• Matthias Schmeisser, Achim Zahl, Andreas Scheurer, Ralph Puchta and Rudi van
Eldik, Ligand Exchange Processes on Solvated Lithium Cations. VI. Determination of
7Coordination Numbers by Ligand Substitution and Li NMR, Z. für Naturforschung B,
2010, 65, 405-413.

• Matthias Schmeisser, Frank W. Heinemann, Peter Illner, Ralph Puchta, Achim Zahl
and Rudi van Eldik, Coordination of 1,10-phenanthroline and 2,2′-bipyridine to Li in
different ionic liquids. How innocent are ionic liquids?, Inorg. Chem., 2011, 50, 6685-

• Thomas M. Klapötke, Jörg Stierstorfer, H. Donald Brooke Jenkins, Rudi van Eldik
and Matthias Schmeisser, Calculation of some thermodynamic properties and
detonation paramters of 1-ethyl-3-methyl-H-imidazolium perchlorate, [emim][ClO ], 4
on the basis of CBS-4M and CHEETAH computations supplemented by VBT
estimates, Z. Anorg. Allg. Chem., 2011, 637, 1308-1313.

• Matthias Schmeisser, Philipp Keil, Jörg Stierstorfer, Axel König, Thomas M.
Klapötke and Rudi van Eldik, An Ionic Liquid Designed for Coordination Chemistry
Revisited: Synthetic routes and safety tests for 1-ethyl-3-methylimidazolium
Perchlorat [emim][ClO ], Eur. J. Inorg. Chem., 2011, DOI: 10.1002/ejic.201100529. 4

• Peter Illner, Ralph Puchta, Matthias Schmeisser and Rudi van Eldik, Gutmann Donor
and Acceptor Numbers for Ionic Liquids, in preparation.

8 Conference Contributions: Posters

III 4-• Kinetik and thermodynamic studies on the reactivity of [(TMPS)Fe (OH)] in ionic
liquid, Inorganic Reaction Mechanisms Group IRMG, England, Oxford, 2009.

• Unexpected influences of ionic liquids on well known systems, DFG-Meeting SPP
1191, Germany, Bamberg, 2009.

• Complex formation reactions of alkaline metal ions studied by NMR and DFT,
Heidelberg Forum of molecular Catalysis, Germany, Heidelberg, 2009.

• Unexpected influences of ionic liquids on well know reaction systems, Winter School
DFG SPP 1191, Germany, Warnemünde, 2009.

• Complex formation of alkaline metals – ionic liquids versus common solvents,
Inorganic Reaction Mechanisms Group IRMG, Germany, Kloster Banz, 2010.

• Mechanistic studies on inorganic reactions in ionic liquids, Conference on molten
salts and Ionic liquids, Euchem 2010, Germany, Bamberg, 2010.

• Sustainable Production of [EMIM][ClO ], Green Solvents, Germany, Berchtesgaden 4

Conference Contributions: Oral Presentations

• Mechanistic behaviour of metal complexes in ionic liquids – Activation of small
molecules in [emim][NTf ], DFG-Meeting SPP 1191, Germany, Bamberg, 2009. 2

• Inorganic reaction mechanisms in ionic liquids, Winter School DFG SPP 1191,
Germany, Warnemünde, 2009.

• Kinetic studies in ionic liquids – problems with impurities and approaches, Erlangen-
Kraków Workshop on Understanding the mechanisms of chemical processes, Poland,
Kraków, 2010.



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