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The strong N–H acid
H[{(C F ) P(O)} N] 2 5 2 2
Salts and ionic liquids

Thesis submitted to the Faculty of Mathematics and Natural Sciences
Bergische Universität Wuppertal
for the Degree of Doctor of Natural Sciences
– Dr. rerum naturalium –

Dana Bejan

November, 2010

Die Dissertation kann wie folgt zitiert werden:

The work described in this thesis was carried out in the Department of Inorganic
Chemistry, University of Wuppertal, under the scientific supervision of Prof. Dr. H.
Willner, during the period of February 2006 – November 2010.

Referee: Prof. Dr. H. Willner
Co-referee: Prof. Dr. F. Mohr

Cu dragoste, so ţului meu
p ărin ţilor mei

I would like to express my sincere gratitude to Prof. Dr. Helge Willner for the opportunity of doing this
PhD in his research group and for his continuous guidance and fruitful advices. I will always be indebted
to him for the rigorous guidance into the science.
I am also deeply grateful to Dr. Nikolai Ignat’ev for his helpful assistance and his insight to resolve
problems during all the stages of the research.
Furthermore, I thank Prof. Dr. Fabian Mohr for evaluating my thesis as co-referee as well as Prof. Dr.
Hans-Josef Altenbach and Prof. Dr. Michael W. Tausch for their acceptance as members of my thesis
examination committee.
A special recognition to Priv.-Doz. Dr. Eduard Bernardt and Prof. Dr. Christian W. Lehmann for X-ray
structural determinations included in my thesis. All thanks to Prof. Dr. Eujen Reint and Priv.-Doz. Dr.
Helmut Beckers for fruitful discussions and suggestions.
Dr. Andriy Kucheryna is acknowledged for his help at begin of my research work.
I am very thankful to Dr. Jane Hübner for part of analytical measurements, to Mrs. Anja Amman for the
conductivity and the cyclic voltammetry measurements, to Dr. Peter Barthen for the elemental analysis, to
Mr. Andreas Siebert for NMR and to Mrs. Melanie Dausend for MS measurements.
My special thanks to Mrs. Marion Litz and Dipl. Ing. Erwin Petrauskas for their help for solving
administrative and technical problems.
The present and past colleagues (André, Markus, Xiaoqing, Lücker, Waldemar, Simone, Torsten, Tamara)
are special in my heart for their friendship and assistance. I thank all the members of Departament of
Inorganic Chemistry for the support.
The financial support of the Merck KGaA is gratefully acknowledged.
My deepest gratitude goes to my family for their support throughout my life.
I owe my loving thanks to my husband Iustinian. Without his love, encouragement and understanding it
would have been imposibble for me to finish this work.

This work was developed in the course of a cooperation project with the Merck KGaA
Company (Darmstadt) on weakly coordinating anions and their applications. The
main target was the preparation of the new strong N-H acids bis[bis(perfluoroalkyl)-
phosphinyl]imides (HFPI), bis(pentafluoroethyl)phosphinyl–(trifluoromethyl)sulfonyl-
imide (HPSI), their salts and ionic liquids as well as the study of their catalytic
properties. Most of the compounds were analysed by NMR, IR and Raman
spectroscopy, mass spectrometry and elemental analysis and in some cases by
single crystal X-ray diffraction. The new ionic liquids were characterized by
measuring their viscosity, density, melting point, thermal properties, electrochemical
stability, conductivity, water and ionic impurities.
The first chapter describes improved syntheses of the precursors of HFPI. By
selective hydrolysing (C F ) PF (n = 2, 4) pure bis(perfluoroalkyl)phosphinic, n 2n+1 3 2
(C F ) P(O)OH, and perfluoroalkylphosphonic, C F P(O)(OH) , acids have been n 2n+1 2 n 2n+1 2
obtained. PhPCl was found to be a suitable reagent to convert the acids into acid 4
In chapter 2 formation of (C F ) P(O)NH by treatment of (C F ) PO with NH at 2 5 2 2 2 5 3 3
low temperature is described. Both precursors (C F ) P(O)Cl and (C F ) P(O)NH 2 5 2 2 5 2 2
were reacted in the presence of Et N to form the salt [Et NH][{(C F ) P(O)} N]. The 3 3 2 5 2 2
free acid was obtained by heating the salt in 100 % H SO in vacuum. Its acidity was 2 4
determined by different methods.
In chapter 3 the preparation of new MFPI salts (M = Li, Na, K, Cs, Ag, Mg, Zn,
La, Eu, Ce, and Yb) is described. LiFPI can be used as an electrolyte for lithium ion
batteries. One important application of lanthanide salts are their use as Lewis acid
HFPI and the Na and K salts are suitable starting materials for the synthesis of
new hydrophobic ionic liquids with the FPI anion as described in chapter 4.
Relationships between their physico-chemical properties and their structures are
discussed. FPI ionic liquids possess advanced properties such as: (i) melting points
below 50 °C; (ii) hydrolytic stability in neutral aqueous solution up to 100 °C; (iii)
thermal stability up to 280 °C; (iv) low viscosity; (v) high electrochemical stability; and
(vi) they can be synthesized from industrially available materials.

In the fifth chapter another strong N–H acid (HPSI) and new ionic liquids with
the PSI anion are presented. The properties of a series of ionic liquids with
asymmetrical perfluoroanions, such as PSI anion, are reported here. The asymmetric
species have significant lower melting points than the corresponding symmetric ionic
liquids. Further properties of these PSI derivatives were also investigated and
compared with related FPI and TFSI derivatives. Furthermore, [Et NH][PSI] was 3
characterized by X-ray crystallography.
The catalytic activity of the HFPI acid and some of its salts were investigated for
acylation reactions of various compounds (with –OH, –NH, –SH functional groups)
and the results are shown in chapter 6.
Finally, the last chapter presents the synthesis and characterization of new
bis(pentafluoroethyl)phosphinic acid amides and hydrazides.

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