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Mechanistic investigations on fast reactions in ionic liquids [Elektronische Ressource] / Svetlana Begel. Betreuer: Rudi van Eldik

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148 pages
Mechanistic investigations on fast reactions in ionic liquids Mechanistische Untersuchungen schneller Reaktionen in ionischen Flüssigkeiten Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Svetlana Begel aus Tscheljabinsk (Russland) Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 26.07.2011 Vorsitzender der Promotionskommission: Prof. Dr. Rainer Fink Erstberichterstatter: Prof. em. Dr. Dr. h.c. mult. Rudi van Eldik Zweitberichterstatter: Prof. Dr. Nicolai Burzlaff - 2 - Die vorliegende Arbeit entstand in der Zeit von Oktober 2006 bis März 2011 am Institut für Anorganische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg. - 3 - Acknowledgements My deepest gratitude is to my supervisor Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik for guiding me through the doctoral program and for all his ideas and fruitful discussions which gave me a jump start in this research direction and greatly helped me in my research endeavours. I thank him for his continuous support and encouragement during my scientific development and for the opportunity to present our achievements internationally.
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Mechanistic investigations on fast reactions
in ionic liquids




Mechanistische Untersuchungen schneller Reaktionen
in ionischen Flüssigkeiten




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


vorgelegt von
Svetlana Begel


aus Tscheljabinsk (Russland)
Als Dissertation genehmigt von der Naturwissenschaftlichen Fakultät der
Friedrich-Alexander-Universität Erlangen-Nürnberg



























Tag der mündlichen Prüfung: 26.07.2011
Vorsitzender der Promotionskommission: Prof. Dr. Rainer Fink
Erstberichterstatter: Prof. em. Dr. Dr. h.c. mult. Rudi van Eldik
Zweitberichterstatter: Prof. Dr. Nicolai Burzlaff
- 2 - Die vorliegende Arbeit entstand in der Zeit von Oktober 2006 bis März 2011 am Institut für
Anorganische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg.
































- 3 - Acknowledgements

My deepest gratitude is to my supervisor Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik for
guiding me through the doctoral program and for all his ideas and fruitful discussions which
gave me a jump start in this research direction and greatly helped me in my research
endeavours. I thank him for his continuous support and encouragement during my scientific
development and for the opportunity to present our achievements internationally. His
everlasting optimism and zeal for problem solving is very contagious and has affected not
only me, but almost all the students who come into contact with him.

I am also thankful to Dr. Peter Illner for his help in a better understanding of the problems and
in developing better solutions, for technical and practical advices, for numerous discussions,
and most of all for his enthusiasm and humour which provide a good and friendly working
environment.

I t h a n k M a t t h i a s S c h m e i s s e r a n d S i m on K e r n , f u r t h e r m e m be r s of ou r “ i on i c l i qu i d
c om m u n i t y ” , f or t h e i r c o nstant support, for practical assistance and for all the fun times in and
out of the lab.

I am grateful to Dr. Jörg Sutter and Dr. Marat M. Khusniyarov for their practical and
theoretical assistance in the measurement of numerous EPR and Mössbauer spectra.

I kindly thank Susanne Hoffmann for the technical support with the various IR measurements.

I would like to acknowledge all collaborators that contributed to the mentioned publications.

Furthermore, I would like to thank all members of the group for their support, the helpful
discussions and the great working atmosphere.

None of this would have been possible without the love and patience of my family. They have
been a constant source of love, concern and strength all these years. Their support and care
helped me overcome setbacks and stay focused on my study. I deeply appreciate their belief
in me.

- 4 -
Publications and Conference Contributions

Publications

1. Illner, Peter; Kern, Simon; Begel, Svetlana; van Eldik, Rudi. “Rapid Ligand
Substitution Reactions in Ionic Liquids Studied by Stopped-flow Technique. ”
Chemical Communications, 2007, 45, 4803-4805.

2. Begel, Svetlana; Illner, Peter; Kern, Simon; Puchta, Ralph; van Eldik, Rudi.
„Mechanistic Studies on Fast Ligand Substitution Reactions of Pt(II) in Different Ionic
Liquids: Role of Solvent Polarity and Ion-Pair Formation. ” Inorganic Chemistry,
2008, 47, 7121-7132.

3. Illner, Peter; Begel, Svetlana; Kern, Simon; Puchta, Ralph; van Eldik, Rudi. “Fast
Substitution Reactions of Pt(II) in Different Ionic Liquids. Reactivity Control by
Anionic Components. ” Inorganic Chemistry, 2009, 48, 588-597.

4. Kern, Simon; Illner, Peter; Begel, Svetlana; van Eldik, Rudi. “Mechanistic Studies on
Fast Ligand Substitution Reactions of a Very Labile Pd(II) Complex in Several Ionic
Liquids. ” European Journal of Inorganic Chemistry, 2010, 29, 4658-4666.

5. Begel, Svetlana; Heinemann, Frank, W.; Stopa, Grzegorz; Stochel, Grazyna; van
Eldik, Rudi. “ T h e c l a s s i c „ br ow n - r i n g ‟ r e a c t i on i n a n e w m e di u m : K i n e t i c s ,
mechanism, and spectroscopy of the reversible binding of nitric oxide to iron(II) in an
i on i c l i qu i d. ” Inorganic Chemistry, 2011, 50, 3946-3958.

6. Begel, Svetlana ; v a n E l di k, R u di . “ T h e r m ody n a m i c a n d ki n e t i c s t u di e s on the
IIIinteraction of Ru (edta) with NO in an i on i c l i qu i d.” Dalton Trans., 2011, 40, 4892-
4897.




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Conference Contributions: Posters

1. SPP 1191 DFG-Meeting, Bamberg, May 30 – June 01, 2007.
“ P h y s i c a l a n d m e c h a ni s t i c i n v e s t i g a t i o n s a n d s t u di e s of f a s t r e a c t i on s i n i on i c l i qu i d s . ”
(S. Begel, P. Illner, S. Kern, R. Puchta, R. van Eldik)

2. SPP 1191 DFG-Meeting, Bamberg, December 12-14, 2007.
“ I n f l u e n c e of I L ‟ s a n i on s on r e a c t i on velocities and me c h a ni s m s . ”
(P. Illner, S. Begel, S. Kern. R. Puchta, R. van Eldik)

3. Inorganic Reaction Mechanisms Group IRMG-37, Barcelona, January 9-12, 2008.
“ M e c h a n i s t i c s t u di e s on f a s t l i g a n d s u bs t i t u t i o n r e a c t i on s i n i on i c l i qu i ds . ”
(S. Begel, P. Illner, S. Kern, R. Puchta, R. van Eldik)

4. SPP 1191 DFG-Meeting, Bamberg, March 04 - 06, 2009.
“ U n e x pe c t e d i n f l u ences of ionic liquids on well- kn ow n s y s t e m s .”
(P. Illner, S. Begel, M. Schmeisser, R. Puchta, R. van Eldik)

5. SPP 1191 DFG-Meeting, Bamberg, November 04 - 06, 2009.
“ U n e x pe c t e d i n f l uences of ionic liquids on well- kn ow n r e a c t i on s y s t e m s .”
(S. Begel, S. Kern, M. Schmeisser, P. Illner, R. van Eldik)

6. Inorganic Reaction Mechanisms Group IRMG-39, Kloster (Monastery) Banz January
7-10, 2010.
“ A n old reaction in a new medium: mechanistic study on the reversible binding of NO
t o i r on ( I I ) i n a n i on i c l i qu i d. ”
(S. Begel, R. van Eldik)

rd7. 3 EuCheMS Chemistry Congress, Nürnberg, August 29 – September 2, 2010.
“A well-known reaction in a new medium: Br ow n r i n g t e s t i n a n i on i c l i qu i d. ”
(S. Begel, F. W. Heinemann, G. Stopa, G. Stochel, R. van Eldik)


- 6 -
Conference Contributions: Oral Presentations

1. SPP 1191 DFG-Meeting, Bamberg, May 30 – June 01, 2007.
“ P h y s i c oc h e m i c a l pr ope r t i e s of i on i c l i qu i d s . ”
(S. Begel, P. Illner, S. Kern, R. Puchta, R. van Eldik)


2. SPP 1191 DFG-Meeting, Bamberg, March 04-06, 2009.
“ M e c h a n i s t i c behaviour of m e t a l c om pl e x e s i n i on i c l i qui ds . ”
(P. Illner, S. Begel, M. Schmeisser, R. van Eldik)

3. Winter School GSMS FAU Erlangen-Nürnberg, Kirchberg, March 16-23, 2009.
“ I on i c l i qu i d s : G r e a t n e w r e a c t i on m e di a .”
(S. Begel, R. van Eldik)

4. Erlangen-Kraków Workshop on Understanding the Mechanisms of Chemical
Processes, Kraków, May 25, 2010.
“ A w e l l -known reaction in a new medium: Brown r i n g t e s t i n a n i on i c l i qu i d. ”
(S. Begel, F. W. Heinemann, G. Stopa, G. Stochel, R. van Eldik)


- 7 -
Abbreviations

Complexes
[Pt(ppp)Cl]Cl chloro(2,2`:6`,2``-terpyridine)platinum(II)chloride
[Pd(ppp)Cl]Cl chloro(2,2`:6`,2``-terpyridine)palladium(II)chloride
[emim] [Fe(dca) Cl] [tetra(1-ethyl-3-methylimidazolium)] 4 5
[chloro(pentadicyanamide)ferrat]
K[Ru(Hedta)Cl] 2H O potassium chloro-(monohydrogen ethylenediamine 2
tetra-acetato)-ruthenium(III) dihydrate

Ionic liquids
[emim][dca] 1-ethyl-3-methylimidazolium dicyanamide
[emim][OTf] 1-ethyl-3-methylimidazolium triflate
[emim][NTf ] 1-ethyl-3-methylimidazolium 2
bis(trifluoromethylsulfonyl)amide
[emim][EtOSO ] 1-ethyl-3-methylimidazolium ethylsulfate 3

Other chemicals
IL ionic liquid
TU thiourea

Units and constants
T temperature
K Kelvin
Pa Pascal
s second
M molar (M = mol/l)
l litre
-10Å Angstrøm (10 m)
m meter
kJ kilojoule
Hz hertz
W watt
B magnetic vector potential
- 8 - T tesla
-1 -1R gas constant (R = 8.314472 J K mol )
-23 -1k Boltzmann constant (k = 1.3806504  10 J K B B
-34h Planck constant (h = 6.62606885  10 J s)

Other abbreviations
RT room temperature
NU nucleophile
sc super critical
eq equilibrium
obs observed
det detection
irr irradiation
on forward reaction
off back reaction
[A] c on c e n t r a t i o n of s u bs t a n c e “ A ”
k , k rate constants 1 2
K equilibrium constant
≠ΔH enthalpy of activation
≠ΔS entropy of activation
≠ΔV volume of activation
ΔH° standard reaction enthalpy
ΔS° standard reaction entropy
ΔV° standard reaction volume
DFT density functional theory
UV ultraviolet
Vis visual
EPR electron paramagnetic resonance
NMR nuclear magnetic resonance
FTIR Fourier transform infrared spectroscopy
ATR attenuated total reflection
E (30) molar transition energy of the standard betaine dye no.30 T
ppm parts per million
 hydrogen bond accepting ability
- 9 -
wavenumber
 wavelength
A absorbance at definite concentration x
t time
S spin of the electron
q spectroscopic splitting factor
(2.0023 for the free electron)
ΔE  quadrupole splitting energy Q
 isomer shift


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