Synthesis of bis(polyfluoroalkylated)imidazolium salts as key intermediates for fluorous NHC ligands

Article abstract of DOI:10.1016/j.jfluchem.2009.07.015

1,3-Bis(polyfluoroalkyl)- and 1-mesityl-3-(polyfluoroalkyl)imidazolium salts differing in the length of a polyfluorinated chain and a non-fluorinated spacer were synthesized as key building blocks for fluorous NHC (N-heterocyclic carbene) ligands. A new a

Full text of DOI:10.1016/j.jfluchem.2009.07.015

Journal of Fluorine Chemistry 130 (2009) 966–973
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis of bis(polyfluoroalkylated)imidazolium salts as key intermediates
for fluorous NHC ligands
a
a
a
b
´
´
´ ˇ
´
ˇ
*
´ˇ
´
Martin Skalicky , Marketa Rybackova , Ondrej Kysilka , Magdalena Kvıcalova ,
c
d
a,
ˇ
ˇ
´ˇ
Josef Cvacka , Jan Cejka , Jaroslav Kvıcala
a
´
Department of Organic Chemistry, Institute of Chemical Technology, Prague, Technicka 5, 16628 Prague 6, Czech Republic
b
c
ˇ
ˇ
ˇ
ˇ
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Husinec-Rez 1001, 25068 Rez, Czech Republic
´
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo nam. 2, 16610 Prague 6, Czech Republic
d
´
Department of Chemistry of Solid State, Institute of Chemical Technology, Prague, Technicka 5, 16628 Prague 6, Czech Republic
A R T I C L E I N F O
A B S T R A C T
Article history:
1,3-Bis(polyfluoroalkyl)- and 1-mesityl-3-(polyfluoroalkyl)imidazolium salts differing in the length of a
polyfluorinated chain and a non-fluorinated spacer were synthesized as key building blocks for fluorous
NHC (N-heterocyclic carbene) ligands. A new approach using polyfluoroalkyl triflates instead of the
corresponding iodides was employed allowing fine tailoring of fluorous properties, as well as of the
electron density of the imidazolium ring. Using bis(polyfluoroalkylated)imidazolium salt, a fluorous
analogue of the PEPPSITM catalyst was synthesized and its structure confirmed by X-ray diffraction. The
catalyst was employed in model Heck and Suzuki couplings with moderate yields, however, its recycle
was not successful. Fluorophilicity of bis(polyfluoroalkylated)imidazolium salts was found to be
surprisingly low compared with the analogous perfluoropolyether-based salts.
Received 22 January 2009
Received in revised form 20 July 2009
Accepted 22 July 2009
Available online 30 July 2009
Keywords:
Imidazolium
Fluorous
Fluorophilic
Triflate
ß 2009 Elsevier B.V. All rights reserved.
Carbene
Mesityl
NHC ligand
1. Introduction
mostly on steric bulk of the substituents surrounding the metal
centers, which significantly improve their stability and activity.
Substituted imidazolium salts are frequently employed as ionic
liquids [1,2] or as a part of biologically active compounds [3–5].
Moreover, they are precursors for the preparation of N-heterocyclic
carbenes, which are a perspective class of compounds used in
medicinal chemistry [6,7] or, even more importantly, as ligands in
homogeneous catalysis [8,9]. Metal complexes derived from NHC
ligands are stable to oxidation and heating to higher temperatures.
1,3-Disubstituted imidazol-2-ylidene complexes of transition
metals have been successfully applied in reactions like Heck, Suzuki,
Sonogashira, Kumada–Tamao–Corriu or Stille coupling [10]. The
most commonly used NHC carbenes contain bulky groups like
cyclohexyl, o-tolyl, mesityl, 2,6-diisopropylphenyl or adamantyl
[11]. The N-substituents have a limited effect on the electronic
density of the carbene carbon [12,13] and even carbenes with
Metal complexes with ligands containing fluorous tags exhibit
special features like the possibility of using fluorous biphase
catalysis or a recovery of the catalyst from the reaction mixture by
means of fluorous solid phase extraction [15]. Surprisingly little is
known about imidazolium salts bearing polyfluorinated chains.
We recently published the synthesis of polyfluoroalkylated
imidazolium salt substituted with branched fluorous polyether
tails, which combined excellent fluorophilicity and ionic liquid
properties [16]. In 2000, Xu et al. reported imidazolium salt 1 with
linear fluorous chains and preparation of palladium NHC complex
thereof [17]. Another fluorous imidazolium salt 2 was reported in
2001 and employed as an intermediate for a light fluorous Grubbs
catalyst analogue [18] (Fig. 1).
In both cases, a perfluorohexyl chain with ethylene spacer was
used and no discussion regarding the role of polyfluorinated
ponytail was included. Several another imidazolium salts bearing
one polyfluoroalkyl and one alkyl ponytail have been synthesized
and employed, e.g. as ionic liquid/fluorocarbon emulsifiers [19]. In
the last few years we oriented our research on the study of fluorous
ligands [20–23]. This inevitably resulted in our aim in fluorous
NHC ligands and the role of the length of the perfluorinated part of
electron-withdrawing groups retain sufficient s-donating ability to
form complexes [14]. Fine tuning of NHC’s properties hence relies
* Corresponding author.
ˇ
E-mail address: kvicalaj@vscht.cz (J. Kvı´cala).
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.07.015

M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
967
Fig. 1. Examples of published fluorous imidazolium salts.
the ponytails. We were also interested in the complexation
properties–electron density relationship depending essentially on
the length of the non-fluorinated spacer. As the first part of our
research results we report here the synthesis of the key precursors
of two classes of target fluorous NHC ligands, 1,3-bis(polyfluor-
oalkyl)- and 1-mesityl-3-(polyfluoroalkyl)imidazolium salts,
together with preliminary results dealing with the preparation
of fluorous PEPPSITM catalyst and its applications in model Heck
and Suzuki reactions.
2. Results and discussion
2.1. 1-(Polyfluoroalkyl)imidazoles 9–12
The preparation of polyfluoroalkylated imidazoles was based on
the reaction of imidazole with polyfluoroalkyl halide or triflate. In
order to neutralize the acid formed, excess of imidazole was used.
For imidazoles containing fluorous ponytail with the ethylene
spacer, commercially available 2-(perfluoroalkyl)ethyl iodides 5,6
were used. Thus, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imida-
zole 11 was obtained according to [17] and (3,3,4,4,5,5,6,6,
7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)imidazole 12 was pre-
pared analogously, both in good yields (Scheme 1). However,
polyfluoroalkyliodideswithmethylenespacerarenotcommercially
available and, moreover, their reactivity is significantly lower [24].
We hence employed instead of the iodides the corresponding
polyfluoroalkyl triflates, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl
triflate (3) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl
triflate (4), prepared from commercially available polyfluorinated
alcohols and trifluoromethanesulfonic anhydride according to
[25,26] and obtained the corresponding 1-polyfluoroalkylated
imidazoles 9 and 10 in excellent yields (Scheme 1).
Scheme 2.
completely. We therefore used the corresponding triflate,
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl triflate
(8), prepared from commercially available fluoroalcohol according
to the procedure developed by us [27]. The second methylene
spacer containing fluorous ponytails was attached similarly using
the above mentioned triflates 3 and 4. As a solvent, toluene was
used in all cases except of the reactions of fluoroalkylated
imidazole 10, the solubility of which was not sufficient and hence
a toluene/DMF mixture had to be used. The target 1,3-disub-
stituted imidazolium salts 13–22 were obtained in moderate to
excellent yields (Scheme 2).
Melting point measurements of imidazolium salts 13–22
revealed two distinguished features: first, imidazolium salts 13,
16, 17 bearing only methylene spacers displayed significantly
higher stability (they melt above 230 8C without decomposition
compared to those with ethylene spacers which decompose above
150 8C); second, more symmetrical imidazolium salts 13, 17
melted at slightly higher temperatures (245 8C and 251 8C,
respectively) compared to non-symmetrical salt 16 (231 8C).
2.2. 1,3-Bis(polyfluoroalkyl)imidazolium salts 13–22
While the first alkylation proceeds smoothly at 80 8C, the
second alkylation giving imidazolium salts requires reflux in
toluene. Whereas we were able to reproduce [17] the reaction of
fluoroimidazole 11 with 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl
iodide (5) in an acceptable 45% yield, we were surprised that the
same reaction using longer 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecyl iodide (6) as the alkylating reagent failed
2.3. 1-Mesityl-3-(polyfluoroalkyl)imidazolium salts 24, 25
The title imidazolium salts bearing one mesityl and one
polyfluoroalkyl substituent should display properties between
the well-known 1,3-dimesitylimidazolium salts [28] and 1,3-
bis(polyfluoroalkyl)imidazolium salts synthesized by us. Their
synthesis paralleling published preparation [18] employed 1-
mesitylimidazole (23) [29] and fluoroalkyl triflates 4 and 7. The
target unsymmetrical imidazolium salts 24, 25 were obtained in
good to excellent yields (Scheme 3).
2.4. Fluorophilicity measurements
We recently reported the synthesis and properties of imida-
zolium salts substituted with two polyfluorinated chains, at least
one of which being based on perfluorinated polyethers [30]. We
found that these salts behave as fluorous ionic liquids with
excellent solubility in perfluorinated solvents and high fluorophi-
licities [31]. In contrast to this, bis(polyfluoroalkylated)imidazo-
lium salts 13–25 showed rather limited solubility in perfluorinated
solvents and, correspondingly, significantly lower values of
Scheme 1.

968
M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
Table 1
Fluorous partition coefficients of selected imidazolium salts in perfluoro(methyl-
cyclohexane)/toluene mixture at 25 8C and their fluorophilicities.
Entry
Compound
Pi(FBS)
fi
1
2
3
4
5
25
24
17
19
14
0.02
0.4
1.3
1.4
2.6
À4
À0.9
0.26
0.34
0.96
Scheme 3.
All calculations were performed with Gaussian 03W program
suite [32] using DFT methods at the PBE1PBE/6-311+G(d,p) level of
theory.
fluorous partition coefficients between perfluoro(methylcyclohex-
ane) and toluene (Table 1).
2.6. Fluorous PEPPSITM analogue 26
Nevertheless, compared to mono(polyfluoroalkylated)imida-
zolium salts 24, 25, bis(polyfluoroalkylated)imidazolium salts can
be regarded as fluorophilic, i.e. having fluorous partition coeffi-
cients larger than 1 and positive fluorophilicities. The length of
perfluorinated segments and the number of CH2-spacers in side-
chains (14: 26 F and 3 CH2; 17: 34 F and 2 CH2; 19: 34 F and 3 CH2)
does not reflect the expected trend of fluorophilicity (i.e. 17–
19 > 14) probably due to experimental difficulties in the precise
determination of partition coefficients of fluorous compounds
which have rather low absolute solubility in the immiscible liquid
phases.
Remarkable difference between the fluorophilicity of imidazo-
lium salts containing perfluoroalkyl chains and those bearing
perfluoropolyether segments can be attributed to relative rigid-
ness of the perfluoroalkyl group compared to more flexible
perfluoropolyether chain. Following that, central ionic part of
fluorous imidazolium salts 13–25 containing only perfluoroalky-
lated segments remains exposed and hence highly fluorophobic in
contrast to salts containing perfluoropolyether chain, which can
probably shield the charged part of imidazolium salt from
perfluorinated solvent.
We prepared fluorous NHC ligand-based complex 26 by
heating polyfluorinated imidazolium salt 1 with PdCl2 and K2CO3
in an excess of 3-chloropyridine in analogy to the original
PEPPSITM catalyst [33]. The product was isolated as an orange
powder in a moderate yield after evaporation of 3-chloropyr-
idine and precipitation of the crude product from dichloro-
methane solution with pentane (Scheme 4). Surprisingly,
elemental analysis of the crystalline product 26 revealed that
the product contains both chloride and iodide anions coordi-
nated to the central palladium atom in a non-stoichiometric
molar ratio of ca. 3:1.
Orange crystals for X-ray diffraction were obtained by
recrystallization from hexane/CH2Cl2 5:1 mixture. X-ray diffrac-
tion analysis confirmed the coordination of fluorous NHC carbene
to the central palladium atom, as well as the non-stoichiometric
content of chloride and iodide anions in the complex molecule
(Fig. 2) [34].
In complex 26, Pd–halogen bonds are oriented nearly perpen-
dicularly to the imidazolylidene ring, whereas 3-chloropyridine
ring approximately bisects the dihedral angle between both
planes. The polyfluoroalkylated ponytails are arranged on the
opposite sides of the imidazolylidene ring in agreement with the
results of the computational studies (vide supra).
2.5. Calculations of model polyfluorinated imidazolium salts
With the aim to find out how the electron density on the
imidazolium ring can be influenced by substitution with
polyfluoroalkyl groups we chose three model imidazolium salts,
viz. 1,3-dimethylimidazolium triflate (A), 1,3-bis(2,2,3,3,3-pen-
tafluoropropyl)imidazolium triflate (B) and 1,3-bis(3,3,4,4,4-
pentafluorobutyl)imidazolium triflate (C) (Fig. 1). Comparison
of mapped electrostatic potentials on the isoelectronic surfaces
of these molecules clearly shows higher positive charge (cyan
colour compared to green colour) on the site of the attack of base
– hydrogen on ring C2 – for pentafluoroethylated systems B and
C. On the other hand, the difference in the acidity of this
hydrogen between molecules B and C differing in the non-
fluorinated spacer length (methylene for B and ethylene for C) is
less apparent.
2.7. Model reactions of fluorous PEPPSITM analogue 26
PEPPSITM catalyst was successfully employed in many reactions
catalyzed with transition metals, e.g. Negishi, Kumada or Suzuki–
Miyaura coupling, yielding the corresponding products in excel-
lent yields [36]. To compare the activity and recyclability of the
complex 26 with the original PEPPSITM we performed two model
reactions, i.e. Suzuki–Miyaura coupling of phenylboronic acid with
4-iodotoluene, and Heck reaction of 4-iodotoluene with oct-1-ene
(Scheme 5).
Although fluorous catalyst 26 was active in both reactions, the
yields of the corresponding reactions were moderate and inferior
to that of the original PEPPSITM catalyst. We were not able to
Scheme 4.

M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
969
Fig. 2. Electrostatic potential mapped on isoelectronic surface for model imidazolium salts (red, negative charge; blue, positive charge).
Fig. 3. ORTEP [35] plot (50% probability) of complex 26.
3. Conclusions
We synthesized a series of fluorous imidazolium salts as the key
intermediates for fluorous NHC ligands. Whereas shorter fluori-
nated ponytails with ethylene spacer could be attached to the
central imidazole ring using commercial 2-(perfluoralkyl)ethyl
iodides, polyfluoroalkyl triflates had to employed in other cases, i.e.
when longer perfluorinated chain and/or methylene spacer were
present. Based on bis(polyfluoroalkylated)imidazolium salt, fluor-
ous analogue of PEPPSITM catalyst was synthesized. Its catalytic
activity in model Suzuki–Miyaura coupling and Heck reaction
proved to be lower than that of the original PEPPSITM. Fluor-
ophilicity of bis(polyfluoroalkylated)imidazolium salts was found
to be substantially lower than that of the corresponding
imidazolium salts containing polyfluoropolyether ponytails.
Scheme 5.
recycle the catalyst using fluorous separation methods. However,
this is not surprising as both complex 26 and the PEPPSITM catalyst
contain 3-chloropyridine as a throwaway ligand. Consequently, no
information about possible recycle of this type of catalysts is
available.
4. Experimental
2.8. Pilot preparations of other complexes of fluorous NHC ligands
Temperature data were uncorrected. NMR spectra were
recorded with a Varian MercuryPlus spectrometer, 1H NMR
spectra at 299.97 MHz and 13C NMR spectra at 75.43 MHz using
residual deuterated solvent signals as the internal standards, 19F
NMR spectra at 282.22 MHz using CCl3F as the internal standard.
Chemical shifts are given in ppm, coupling constants in Hz. FTIR
spectra were recorded with an FTIR Nicolet 6700 instrument. Mass
spectra (ESI, APCI) were measured with a LCQ Fleet (Finnigan)
instrument, HRMS spectra (ESI, APCI, FAB) with a LTQ Orbitrap XL
(Thermo Fisher Scientific) or ZAB-EQ (VG Analytical) instruments.
All reactions were performed in dry argon atmosphere in an
oven-dried apparatuses. Fluorous separations were accomplished
In recent preliminary experiments, we also synthesized a series
of Ag and Cu complexes based on fluorous NHC ligands 13–22, 24
and 25, and confirmed their structure by NMR and MS experiments
(Fig. 3). These resultswillbepublishedinthefollowingpaperassoon
as good quality crystals for X-ray analysis will be obtained (Fig. 4).
using FluoroFlash1 silica gel (40
ogies, Inc.).
mm grading, Fluorous Technol-
2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl triflate (3), 2,2,3,3,
4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl triflate (4), 3,3,4,4,
5,5,6,6,7,7,8,8,8-tridecafluorooctyl triflate (7) and 3,3,4,4,5,5,
6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl triflate (8) were
Fig. 4. Examples of fluorous NHC complexes recently synthesized in our laboratory.

970
M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
prepared from commercially available alcohols and trifluorometha-
nesulfonic anhydride (triflic anhydride), all purchased from
Apollo Scientific, following published procedures [25–27]. 1-
(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)imidazole (11) and 1,3-
bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium iodide
(1) were prepared according to [17], 1-mesitylimidazole (23)
according to [29]. 1,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iodooc-
tane (5) and 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-
iododecane (6) were kindly donated by Atochem. Imidazole was
purchased from Fluka. Ethyl acetate and DMF were distilled from
P2O5, toluene was stored over Na and distilled prior to use.
7.53 (s 1H). 13C NMR (CDCl3):
d
33.0 (t, 2JCF = 22 Hz), 38.9, 104–119
(m), 118.5, 130.4, 137.1. 19F NMR (CDCl3):
d
À80.9 (t, 3F,
3JFF = 10 Hz), À114.4 (bs, 2F), À121.8 (bs, 2F), À122.1 (bs, 4F),
À122.9 (bs, 2F), À123.6 (bs, 2F), À126.3 (bs, 2F). MS (ESI), m/z (%):
[M+H]+ 515 (100). HRMS (ESI), calcd for C13H7F17 N2 [M+H]+,
515.0411; found 515.0409. IR (neat)
(m), 1216 (s), 1195 (s), 1175 (s), 1199 (s).
n 3199 (w), 3103 (w), 1513
4.5. Preparation of imidazolium salts—General procedure A
Polyfluoroalkylated imidazole and polyfluoroalkyl triflate were
mixed in a Schlenk flask. Toluene was added and the mixture was
stirred for specified time at 100 8C. After evaporating toluene on
rotary vacuum evaporator (40 8C/2 h/2 kPa), the crude product was
dissolved in a small amount of EtOAc and precipitated with 10-fold
excess of hexane. Obtained crystals were decanted and washed
with hexane. Traces of solvents were removed from the product by
vacuum (r.t./2 h/100 Pa).
4.1. Preparation of polyfluorinated imidazoles—General procedure
Polyfluorinated triflate or iodide and imidazole were dissolved
in dry EtOAc. Reaction was heated for specified time. After cooling
to room temperature, organic phase was washed with water and
combined water layers were extracted with EtOAc. Combined
organic phases were dried with anhydrous magnesium sulfate,
solvents were removed by rotary vacuum evaporator and crude
product either recrystallized from hexane/EtOAc 20:1 mixture or
purified by fluorous solid phase extraction (fluorophobic wash
with MeOH/H2O 4:1, fluorous wash with MeOH).
4.6. Preparation of imidazolium salts—General procedure B
Polyfluoroalkylated imidazole and polyfluoroalkyl triflate were
mixed in a Schlenk flask. Toluene and DMF were added and the
mixture was stirred for specified time at 100 8C. After evaporating
bulk of solvents on a rotary vacuum evaporator (60 8C/2 h/2 kPa), a
methanol/water mixture was added and the precipitate formed
was filtered off. The crude product was dissolved in a small amount
of EtOAc and precipitated with 10-fold excess of hexane. Obtained
crystals were decanted and washed with hexane. Traces of solvents
were removed from the product by vacuum (r.t./2 h/100 Pa).
4.2. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)imidazole (9)
A reaction mixture containing triflate 3 (1.00 g, 2 mmol,
1 equiv.) and imidazole (0.420 g, 6 mmol, 3 equiv.) in 30 ml of
EtOAc was stirred for 3 d at 80 8C. After extraction (2Â 30 ml of
water, 10 ml of EtOAc) and recrystallization, 0.79 g of product 9
(98.7%, white crystals, m.p. 88.6–90.9 8C) was obtained. 1H NMR
(CDCl3):
d
4.56 (t, 2H, 3JHF = 15.0 Hz), 6.96 (s, 1H), 7.10 (s, 1H), 7.51
4.7. 1,3-Bis(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)imidazolium
2
(s, 1H). 13C NMR (CDCl3):
d
46.5 (t, JCF = 24 Hz), 105–120 (m),
triflate (13)
120.2; 130.0; 138.5. 19F NMR (CDCl3):
d
À81.2 (bs, 3F), À117.8 (bs,
2F), À122.0 (bs, 2F), À123.0 (bs, 2F), À123.4 (bs, 2F), À126.4 (bs,
A mixture of fluoroimidazole 9 (2.80 g, 6.9 mmol, 1.0 equiv.)
and triflate 3 (3.71 g, 7.7 mmol, 1.1 equiv.) in 100 ml of toluene
was stirred for 72 h at 100 8C. Following the General procedure A
(40 ml of EtOAc, 150 ml of hexane, washed with 20 ml of hexane)
2.76 g of product 13 (44.7%, grey powder, m.p. 244.5–246.1 8C) was
2F). MS (ESI), m/z (%): [M+H]+ 401 (100). HRMS (ESI), calcd for
C
10H6N2F13 [M+H]+, 401.0318; found 401.0318. IR (neat)
n 3129
(w), 3098 (w), 1517 (m), 1237 (s), 1211 (s), 1192 (s), 1151 (s).
4.3. 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-
obtained. 1H NMR (aceton-d6):
2H), 9.85 (s, 1H). 13C NMR (aceton-d6):
120 (m); 126.4, 142.1. 19F NMR (aceton-d6):
d
5.77 (t, 4H, 3JHF = 15.0 Hz), 8.25 (s,
49.6 (t, 2JCF = 22 Hz), 110–
À77.9 (s, 3F), À80.5
Heptadecafluorononyl)imidazole (10)
d
d
A reaction mixture containing triflate 4 (3.00 g, 5.10 mmol,
1.0 equiv.) and imidazole (1.07 g, 15.3 mmol, 3 equiv.) in 100 ml of
EtOAc was stirred for 3 d at 80 8C. After extraction (3Â 30 ml of
water, 20 ml of EtOAc) and recrystallization, 2.47 g of product 10
(96.8%, light brown crystals, m.p. 97.6–99.1 8C) was obtained. 1H
(bs, 6F), À116.5 (bs, 4F), À121.2 (bs, 4F), À122.1 (bs, 8F), À125.5
(bs, 4F). MS (ESI), m/z (%): 733 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C17H7F26N2 [MÀTfOÀ]+, 733.0189; found
733.0193. IR (neat) n 3158 (w), 3043 (w), 3012 (w), 1576 (w), 1243
(s), 1214 (s), 1149 (s).
NMR (CDCl3):
7.56 (s 1H). 13C NMR (CDCl3):
d
4.57 (t, 2H, 3JHF = 15.0 Hz), 7.01 (s, 1H), 7.15 (s, 1H),
d
45.7 (t, 2JCF = 23 Hz), 110–122 (m),
4.8. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)-3-
3
115.4, 125.7, 129.6. 19F NMR (CDCl3):
d
À81.2 (t, 3F, JFF = 9 Hz),
(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate (14)
À118.0 (bs, 2F), À122.3 (bs, 6F), À123.4 (bs, 4F), À126.6 (bs, 2F). MS
(ESI), m/z (%): [M+H]+ 501 (100). HRMS (ESI), calcd for C12H6F17 N2
A mixture of fluoroimidazole 9 (700 mg, 1.75 mmol, 1.0 equiv.)
and triflate 7 (868 mg, 1.75 mmol, 1.0 equiv.) in 20 ml of toluene
was stirred for 72 h at 100 8C. Following the General procedure A
(3 ml of EtOAc, 30 ml of hexane, washed with 10 ml of hexane)
1.36 g of product 14 (86.7%, brown powder, 150 8C dec) was
[M+H]+, 501.0254; found 501.0254. IR (neat)
1517 (m), 1229 (s), 1179 (s), 1160 (s).
n 3128 (w), 3099 (w),
4.4. 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluorodecyl)imidazole (12)
obtained. 1H NMR (acetone-d6):
d 3.22 (m, 2H), 5.00 (t, 2H,
3JHH = 7.1 Hz), 5.63 (t, 2H, 3JHF = 15.8 Hz), 8.09 (s, 1H), 8.18 (s, 1H),
2
A reaction mixture containing 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-
heptadecafluoro-10-iododecane (6, 500 mg, 0.871 mmol,
9.66 (s, 1H). 13C NMR (acetone-d6):
d
31.9 (t, JCF = 20 Hz), 43.8,
2
49.1 (t, JCF = 26 Hz), 115–120 (m); 124.7; 126.0; 140.7. 19F NMR
1.0 equiv.) and imidazole (148 mg, 2.18 mmol, 2.5 equiv.) in
40 ml of EtOAc was stirred for 5 d at 80 8C. After extraction (2Â
30 ml of water, 20 ml of EtOAc) and purification by fluorous solid
phase extraction, 300 mg of product 12 (66.9%, light brown
(acetone-d6):
d
À78.0 (s, 3F), À80.6 (bs, 6F), À113.2 (bs, 2F), À116.5
(bs, 2F), À121.4 (bs, 4F), À122.2 (bs, 6F), À123.0 (bs, 2F), À125.7
(bs, 4F). MS (ESI), m/z (%): 747 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C18H9F26N2 [MÀTfOÀ]+, 747.0345; found
crystals, m.p. 107.6–109.2 8C) was obtained. 1H NMR (CDCl3):
d
747.0350. IR (neat)
(s), 1214 (s), 1150 (s).
n 3154 (w), 3122 (w), 3070 (w), 1569 (w), 1240
3
2.59 (m, 2H), 4.30 (t, 2H, JHH = 7.0 Hz), 6.94 (s, 1H), 7.10 (s, 1H),

M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
971
3
4.9. 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl)-3-
9.64 (s, 1H). 13C NMR (acetone-d6):
d
30.9 (t, JCF = 21 Hz), 42.8,
48.2 (t, JCF = 21 Hz), 106–119 (m), 123.9, 125.0, 139.7. 19F NMR
(acetone-d6):
3
(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)imidazolium triflate (15)
d
À78.2 (s, 3F), À80.6 (bs, 6F), À113.3 (bs, 2F), À116.5
A mixture of fluoroimidazole 9 (230 mg, 0.57 mmol, 1.0 equiv.)
and triflate 8 (350 mg, 0.57 mmol, 1.0 equiv.) in 20 ml of toluene
was stirred for 72 h at 100 8C. Following the General procedure A
(3 ml of EtOAc, 30 ml of hexane, washed with 10 ml of hexane)
531 mg of product 15 (92.7%, brown powder, 150 8C dec) was
(bs, 2F), À121.3 (bs, 8F), À122.1 (bs, 4F), À122.4 (bs, 2F), À123.0
(bs, 2F), À125.7 (bs, 4F). MS (ESI), m/z (%): 847 [MÀTfOÀ]+ (100),
149 [TfO]À (100). HRMS (ESI), calcd for C20H9F30N2 [MÀTfO]+,
847.0281; found 847.0286. IR (neat)
n 3154 (w), 3122 (w), 3070
(w), 1571 (w), 1280 (s), 1224 (s), 1171 (s), 1154 (s).
obtained. 1H NMR (acetone-d6):
d 3.21 (m, 2H), 5.00 (t, 2H,
3JHH = 7.1 Hz), 5.63 (t, 2H, 3JHF = 15.8 Hz), 8.09 (s, 1H), 8.19 (s, 1H),
4.13. 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl)-3-
(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)imidazolium
triflate (19)
9.65 (s, 1H). 13C NMR (acetone-d6):
d
32.4 (t, JCF = 20 Hz), 44.3,
2
2
49.7 (t, JCF = 23 Hz), 114–120 (m), 125.5, 126.6, 141.1. 19F NMR
(acetone-d6):
d
À78.1 (s, 3F), À80.6 (bs, 6F), À113.2 (bs, 2F), À116.5
(bs, 2F), À121.4 (bs, 8F), À122.2 (bs, 6F), À123.0 (bs, 2F), À125.6
(bs, 4F). MS (ESI), m/z (%): 847 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C20H9F30N2 [MÀTfO]+, 847.0281; found
A
mixture of fluoroimidazole 10 (300 mg, 0.60 mmol,
1.0 equiv.) and triflate (358 mg, 0.60 mmol, 1.0 equiv.) in
8
10 ml of toluene and 1 ml of DMF was stirred for 48 h at 100 8C.
Following the General procedure B (8 ml of methanol with 2 ml of
water, followed by 2 ml of EtOAc, 20 ml of hexane, washed with
5 ml of hexane) 384 mg of product 19 (58.5%, white powder, 150 8C
847.0286. IR (neat) n 3154 (w), 3122 (w), 3070 (w), 1569 (w), 1243
(m), 1194 (s), 1179 (s), 1145 (s).
4.10. 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorononyl)-3-
dec) was obtained. 1H NMR (acetone-d6):
d 3.19 (m, 2H), 4.97 (t, 2H,
(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)imidazolium triflate (16)
3JHH = 7.0 Hz), 5.60 (t, 2H, 3JHF = 15.5 Hz), 8.05 (s, 1H), 8.16 (s, 1H),
3
9.63 (s, 1H). 13C NMR (acetone-d6):
d
32.5 (t, JCF = 21 Hz), 44.4,
2
A
mixture of fluoroimidazole 10 (324 mg, 0.65 mmol,
49.7 (t, JCF = 23 Hz), 106–122 (m), 125.4, 126.7, 141.3. 19F NMR
1.0 equiv.) and triflate (310 mg, 0.65 mmol, 1.0 equiv.) in
3
(acetone-d6):
d
À78.2 (s, 3F), À80.7 (bs, 6F), À113.3 (bs, 2F), À116.5
10 ml of toluene and 1 ml of DMF was stirred for 48 h at 100 8C.
Following the General procedure B (8 ml of methanol with 2 ml of
water, followed by 2 ml of EtOAc, 20 ml of hexane, washed with
5 ml of hexane) 468 mg of product 16 (73.6%, white powder, m.p.
(bs, 2F), À121.4 (bs, 12F), À122.2 (bs, 6F), À122.9 (bs, 2F), À125.7
(bs, 4F). MS (ESI), m/z (%): 947 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C22H9F34N2 [MÀTfO]+, 947.0217; found
947.0224. IR (neat) n 3154 (w), 3124 (w), 3069 (w), 1569 (w), 1263
229.5–232.3) was obtained. 1H NMR (acetone-d6):
3JH–F = 15.8 Hz), 8.21 (s, 2H), 9.81 (s, 1H). 13C NMR (acetone-d6):
50.1 (t, 2JCF = 22 Hz), 106–125 (m); 127.0, 142.9. 19F NMR (acetone-
d
5.71 (t, 4H,
(s), 1230 (s), 1155 (s).
d
4.14. 1,3-Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium
d6):
d
À78.3 (s, 3F), À80.5 (bs, 6F), À116.5 (bs, 4F), À121.2 (bs, 8F),
triflate (20)
À122.2 (bs, 8F), À125.7 (bs, 4F). MS (ESI), m/z (%): 833 [MÀTfOÀ]+
(100), 149 [TfO]À (100). HRMS (ESI), calcd for C19H7F30N2
A
mixture of fluoroimidazole 11 (576 mg, 1.18 mmol,
[MÀTfO]+, 833.0125; found 833.0131. IR (neat)
n
3151 (w),
1.0 equiv.) and triflate (490 mg, 1.18 mmol, 1.0 equiv.) in
7
3127 (w), 3039 (w), 1574 (w), 1247 (s), 1197 (s), 1193 (s).
20 ml of toluene was stirred for 48 h at 100 8C. Following the
General procedure A (2 ml of EtOAc, 20 ml of hexane, washed with
another 10 ml of hexane) 872 mg of product 20 (80.9%, light brown
4.11. 1,3-Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-
heptadecafluorononyl)imidazolium triflate (17)
powder, 150 8C dec) was obtained. 1H NMR (acetone-d6):
d
3.11 (m,
4H), 4.85 (t, 4H, JHH = 7.0 Hz), 8.01 (s, 2H), 9.47 (s, 1H). 13C NMR
3
2
A
mixture of fluoroimidazole 10 (300 mg, 0.60 mmol,
(acetone-d6):
138.1. 19F NMR (acetone-d6):
d
31.0 (t, JCF = 21 Hz), 42.2, 104–122 (m), 123.4,
1.0 equiv.) and triflate (350 mg, 0.60 mmol, 1.0 equiv.) in
4
d
À78.2 (s, 3F), À80.8 (t, 6F,
10 ml of toluene and 1 ml of DMF was stirred for 48 h at 100 8C.
Following the General procedure B (8 ml of methanol with 2 ml of
water, followed by 2 ml of EtOAc, 20 ml of hexane, washed with
5 ml of hexane) 299 mg of product 17 (46.0%, white powder, m.p.
252.0–254.7 8C) was obtained. 1H NMR (acetone-d6):
3JHF = 14.4 Hz), 7.96 (s, 1H), 8.22 (s, 1H), 9.82 (s, 1H). 13C NMR
(acetone-d6):
48.7 (t, 3JCF = 23 Hz), 110–120 (m), 125.6, 141.4. 19
NMR (acetone-d6):
4JFF = 10 Hz), À113.4 (bs, 4F), À121.4 (bs, 4F), À122.4 (bs, 4F),
À123.0 (bs, 4F), À125.8 (bs, 4F). MS (ESI), m/z (%): 761 [MÀTfOÀ]+
(100), 149 [TfO]À (100). HRMS (ESI), calcd for C19H11F26N2
[MÀTfO]+, 761.0502; found 761.0504. IR (neat)
n 3149 (w), 3120
d
5.72 (t, 4H,
(w), 3070 (w), 1573 (m); 1347 (s), 1227 (s), 1178 (s), 1142 (s), 1124
(s).
d
F
d
À78.1 (s, 3F), À80.5 (bs, 6F), À116.4 (bs, 4F),
4.15. 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl)-3-
À121.2 (bs, 12F), À122.1 (bs, 8F), À125.6 (bs, 4F). MS (ESI), m/z (%):
(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate (21)
933 [MÀTfOÀ]+ (100), 149 [TfO]À (100). HRMS (ESI), calcd for
C
21H7F34N2 [MÀTfO]+, 933.0061; found 933.0067. IR (neat)
n
3135
A mixture of fluoroimidazole 11 (830 mg, 2.00 mmol,
(w), 3048 (w), 2986 (w), 1574 (w), 1231 (s), 1158 (s).
1.0 equiv.) and triflate 8 (1.20 g, 2.00 mmol, 1.0 equiv.) in 30 ml
of toluene was stirred for 48 h at 100 8C. Following the General
procedure A (3 ml of EtOAc, 30 ml of hexane, washed with 10 ml of
hexane) 1.98 g of product 21 (98.9%, grey powder, 170 8C dec) was
4.12. 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorononyl)-3-
(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium triflate (18)
obtained. 1H NMR (acetone-d6):
d 3.10 (m, 4H), 4.85 (t, 4H,
A
mixture of fluoroimidazole 10 (300 mg, 0.60 mmol,
3JHH = 6.8 Hz), 8.00 (s, 2H), 9.46 (s, 1H). 13C NMR (acetone-d6):
d
2
1.0 equiv.) and triflate (298 mg, 0.60 mmol, 1.0 equiv.) in
7
32.9 (t, JCF = 20 Hz), 43.8, 107–126 (m), 125.0; 139.8. 19F NMR
10 ml of toluene and 1 ml of DMF was stirred for 48 h at 100 8C.
Following the General procedure B (8 ml of methanol with 2 ml of
water, followed by 2 ml of EtOAc, 20 ml of hexane, washed with
5 ml of hexane) 391 mg of product 18 (65.4%, white powder, 180 8C
(acetone-d6):
d
À79.7 (s, 3F), À82.5 (bs, 6F), À115.0 (bs, 4F), À122.8
(bs, 4F), À123.0 (bs, 4F), À124.0 (bs, 4F), À124.5 (bs, 4F), À127.5
(bs, 4F). MS (ESI), m/z (%): 861 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C21H11F30N2 [MÀTfO]+, 861.0438; found
dec) was obtained. 1H NMR (acetone-d6):
d
3.19 (m, 2H), 4.97 (t, 2H,
861.0443. IR (neat)
(s), 1193 (s), 1176 (s), 1142 (s).
n 3153 (w), 3118 (w), 3070 (w), 1553 (w), 1248
3JHH = 7.0 Hz), 5.61 (t, 2H, 3JHF = 15.8 Hz), 8.05 (s, 1H), 8.17 (s, 1H),

972
M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
4.16. 1,3-Bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
4.20. Example of fluorous partition coefficient measurement:
heptadecafluorodecyl)imidazolium triflate (22)
estimation of fluorophilicity of imidazolium salt 19
A mixture of fluoroimidazole 12 (100 mg, 0.2 mmol, 1.0 equiv.)
and triflate 8 (120 mg, 0.2 mmol, 1.0 equiv.) in 10 ml of toluene
was stirred for 30 h at 100 8C. Following the General procedure A
(1 ml of EtOAc, 10 ml of hexane, washed with another 5 ml of
hexane), 200 mg of product 22 (90.3%, grey powder, 150 8C dec)
Using 10.05 mg of fluorous imidazolium salt 19, 0.5 ml of
toluene and 0.5 ml of perfluoro(methylcyclohexane) (PFMC),
0.13 mg and 0.09 mg of imidazolium salt 19 were obtained after
equilibration from the 0.25 ml portions of the respective PFMC and
toluene layers, which corresponds to Pi(FBS) = 1.4 and fi = 0.34.
was obtained. 1H NMR (acetone-d6):
d 3.15 (m, 4H), 4.90 (t, 4H,
3JHH = 7.0 Hz), 8.02 (s, 2H), 9.51 (s, 1H). 13C NMR (acetone-d6):
d
4.21. Dichloro[(1,3-bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-
2
32.7 (t, JCF = 20 Hz), 44.0, 108–122 (m), 125.1, 139.6. 19F NMR
1,3-dihydroimidazol-2-ylidene](3-chloropyridine)palladium(II) (26)
(acetone-d6):
d
À78.0 (s, 3F), À80.6 (bs, 6F), À113.2 (bs, 4F), À121.0
(bs, 4F), À121.2 (bs, 8F), À122.1 (bs, 4F), À123.0 (bs, 4F), À125.9
(bs, 4F). MS (ESI), m/z (%): 961 [MÀTfOÀ]+ (100), 149 [TfO]À (100).
HRMS (ESI), calcd for C23H11F34 N2 [MÀTfOÀ]+, 961.0374; found
In a Schlenk flask, 1,3-bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluor-
ooctyl)imidazolium iodide (1, 530 mg, 0.596 mmol, 1.1 equiv.),
PdCl2 (90 mg, 0.51 mmol, 1.0 equiv.) and K2CO3 (350 mg,
2.53 mmol, 5.0 equiv.) were mixed and 3-chloropyridine (2 ml)
was added. The mixture was stirred for 48 h at 90 8C. After cooling to
roomtemperaturethe reactionmixturewas dilutedwithCH2Cl2 and
passed through a short pad of silica covered with a pad of celite.
CH2Cl2 was removed by rotary evaporator (30 8C/2 h/2 kPa) and 3-
chloropyridine was removed by vacuum destilation (32 8C/400 Pa)
forfurther reuse. Afterdissolvingthe solidinsmallamount ofCH2Cl2
(0.5 ml), precipitation with pentane (5 ml), decanting and drying in
vacuum (25 8C/12 h/100 Pa), 213 mg of complex 26 (39.9%, orange
powder) was obtained. Crystals for X-ray diffraction were obtained
961.0377. IR (neat) n 3154 (w), 3121 (w), 3073 (w), 1573 (w), 1251
(m), 1198 (s), 1178 (s), 1146 (s).
4.17. 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorononyl)-3-
mesitylimidazolium triflate (24)
A mixture of 1-mesitylimidazole (23, 345 mg, 1,85 mmol,
1.0 equiv.) and triflate 4 (1078 mg, 1.85 mmol, 1.0 equiv.) in
30 ml of dry toluene was stirred for 72 h at 100 8C. Following the
General procedure A (7 ml of EtOAc, 30 ml of hexane, washed
with 10 ml of hexane) 1.17 g of product 24 (81.8%, light pink
crystals, m.p. 155.2–156.3) was obtained. 1H NMR (acetone-d6):
by recrystallization (hexane/CH2Cl2 5:1). 1H NMR (CDCl3):
4H), 4.92 (m, 4H), 7.58 (s, 2H), 7.64 (m, 1H), 8.15 (m, 1H), 8.94 (m,
1H), 9.00(m, 1H). 13C NMR (CDCl3): 31.8(t, 2JCF = 21 Hz), 43.8, 115–
120 (m); 122.8; 125.0; 132.8; 138.1; 150.7; 151.8. 19F NMR (CDCl3):
d3.30 (m,
d
2.12 (s, 6H), 2.38 (s, 3H), 5.78 (t, 2H, 3JHF = 15.8 Hz), 7.18 (s, 2H),
8.11 (s, 1H), 8.38 (s, 1H), 9.70 (s, 1H). 13C NMR (acetone-d6):
16.5, 20.4, 48.6 (t, 2JCF = 23 Hz), 105–120 (m), 125.2, 125.7, 129.8,
131.2, 134.7, 140.1, 141.6. 19F NMR (acetone-d6):
d
d
d
À80.5 (bs, 6F), À112.8 (bs, 4F), À121.2 (bs, 4F), À122.3 (bs, 4F),
d
À77.9 (s, 3F),
À122.8 (bs, 4F), À125.6 (bs, 4F). MS (ESI), m/z (%): 1166
À80.5 (t, 3F, 3JFF = 10 Hz), À116.4 (bs, 2F), À121.1 (bs, 6F), À122.0
(bs, 4F), À125.6 (bs, 2F). MS (ESI), m/z (%): [MÀTfOÀ]+ 619 (100);
TfOÀ 149 (100). HRMS (ESI), calcd for C21H16F17N2 [MÀTfO]+,
[C24H14Cl2F26IN3NaPd]À (100), 1072 [C24H14Cl3F26N3NaPd]À (97).
4.22. Model Suzuki–Miyaura coupling catalyzed with complex 26
619.1037; found 619.1038. IR (neat)
n 3186 (w), 3118 (w), 3033
(w), 2986 (w), 1565 (w), 1554 (w), 1280 (s), 1296 (s), 1248 (s),
1214 (s), 1161 (s).
Phenylboronic acid (100 mg, 0.82 mmol, 1.2 equiv.) and 4-
iodotoluene (149 mg, 0.68 mmol, 1.0 equiv.) were dissolved in
dioxane (6 ml). K2CO3 (280 mg, 2.03 mmol, 3 equiv.) and complex
4.18. 1-Mesityl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-
26 (15 mg, 10 mmol, 2%) were added and the reaction mixture was
tridecafluorooctyl)imidazolium triflate (25)
stirred at 80 8C overnight. After cooling to r.t. the reaction mixture
was diluted with 15 ml of Et2O and filtered through short pad of
silica. After evaporating the solvents (40 8C/2 h/2 kPa), 4-methyl-
biphenyl (62 mg, 54%, white crystals) was isolated by column
chromatography (eluent hexane/CH2Cl2 3:1), 1H NMR spectrum of
which was identical with the published values [37]
A mixture of 1-mesitylimidazole (23, 482 mg, 2.58 mmol,
1.0 equiv.) and triflate 7 (1.28 g, 2.58 mmol, 1.0 equiv.) in 30 ml
of dry toluene was stirred for 72 h at 100 8C. 1.71 g of product 25
(96.8%, colorless oil) was obtained. 1H NMR (acetone-d6):
d
2.10 (s,
3
6H), 2.36 (s, 3H), 3.29 (m, 2H), 5.02 (t, 2H, JHH = 7.1 Hz), 7.15 (s,
2H), 7.93 (s, 1H), 8.31 (s, 1H), 9.48 (s, 1H) 13C NMR (acetone-d6):
d
4.23. Model Heck reaction catalyzed with complex 26
2
16.6, 20.3, 31.0 (t, JCF = 21 Hz), 108–122 (m), 124.1, 124.6, 129.7,
131.5, 134.9, 138.3, 141.2 19F NMR (acetone-d6):
d
À77.9 (s, 3F),
4-Iodotoluene (300 mg, 1.37 mmol, 1.0 equiv.) and oct-1-ene
(170 mg, 1.52 mmol, 1.1 equiv.) were dissolved in 15 ml of dry DMF.
Complex 26 (28 mg, 0.03 mmol, 0.02 equiv.), n-Bu4NBr (5 mg,
0.01 mmol, 0.01 equiv.) and AcONa (147 mg, 1.79 mmol, 1.3 equiv.)
were added and the reaction mixture was heated to 120 8C for 48 h.
After cooling to r.t., 50 ml of Et2O was added and the organic layer
was washed three times with 30 ml of water. After drying with
anhydrous MgSO4, filtration and evaporating the solvents (60 8C/
2 h/1.5 kPa), 4-oct-1-enyltoluene (166 mg, 60%, colourless oil) was
isolated by column chromatography (eluent hexane), 1H NMR
spectrum of which was identical with the published values [38].
À80.5 (t, 3F, 3JFF = 10 Hz), À113.2 (bs, 2F), À121.3 (bs, 2F), À122.3
(bs, 2F), À122.9 (bs, 2F), À125.7 (bs, 2F). MS (ESI), m/z (%): 533
[MÀTfOÀ]+ (100), 149 [TfO]À (100). HRMS (ESI), calcd for
C
20H18F13N2 [MÀTfO]+, 533.1257; found 533.1256. IR (neat)
n
3139 (w), 3101 (w), 1568 (w), 1553 (w), 1245 (s), 1225 (s), 1202 (s),
1162 (s), 1144 (s).
4.19. Measurements of fluorous partition coefficient—General
procedure
A 1.5 ml vial equipped with a magnetic stirbar was loaded with
a known quantity of fluorous compound (10 mg), perfluorinated
solvent (0.5 ml) and a non-fluorinated solvent (0.5 ml). The
mixture was stirred while termostatted at 25 8C for 1 h, then
the stirring was stopped. After 0.5 h of standing at 25 8C 0.25 ml of
each layer was removed, evaporated (40 8C/1 h/2 kPa) and
weighed precisely.
Acknowledgements
We thank the Grant Agency of the Czech Republic (Grant No.
203/06/1511) and the Ministry of Education, Youth and Sports
(Research Centre LC 06070, Research Projects Nos. 6046137301
and 6046137302) for financial support.

M. Skalicky´ et al. / Journal of Fluorine Chemistry 130 (2009) 966–973
973
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References
[22] J. Kvı´cala, T. Brıza, O. Paleta, J. Cermak, Tetrahedron 58 (2002) 3847–3854.
[23] T. Brıza, J. Kvıcala, O. Paleta, Collect. Czech. Chem. Commun. 68 (2003) 1039–
1045.
[1] T. Welton, Chem. Rev. 99 (1999) 2071–2083.
[24] T. Umemoto, Y. Gotoh, J. Fluorine Chem. 31 (1986) 231–236.
[25] D. Prescher, T. Thiele, R. Ruhmann, J. Fluorine Chem. 79 (1996) 145–148.
[26] J.L. Alvey, D. Rutherford, J.J. Juliette, J.A. Gladysz, J. Org. Chem. 63 (1998) 6302–
6308.
[2] J. Dupont, R.F. de Souza, P.A.Z. Suarez, Chem. Rev. 102 (2002) 3667–3692.
[3] P.J. Barnard, M.V. Baker, S.J. Berners-Price, D.A. Day, J. Inorg. Biochem. 98 (2004)
1642–1647.
[4] A. Casini, G. Mastrobuoni, M. Terenghi, C. Gabbiani, E. Monzani, G. Moneti, L.
Casella, L. Messori, J. Biol. Inorg. Chem. 12 (2007) 1107–1117.
[5] C.D. Bedford, R.N. Harris III, R.A. Howd, D.A. Goff, G.A. Koolpe, M. Petesch, I.
Koplovitz, W.E. Sultan, H.A. Musallam, J. Med. Chem. 32 (1989) 504–516.
[6] H. Miyachi, H. Kiyota, M. Segawa, Bioorg. Med. Chem. Lett. 9 (1999) 3003–3008.
[7] S. Ray, R. Mohan, J.K. Singh, M.K. Samantaray, M.M. Shaikh, D. Panda, P. Ghosh, J.
Am. Chem. Soc. 129 (2007) 15042–15053.
[8] S.P. Nolan (Ed.), N-Heterocyclic Carbenes in Synthesis, Wiley–VCH, Weinheim,
2006.
[9] L. Cavallo, A. Correa, C. Costabile, H. Jacobsen, J. Organomet. Chem. 690 (2005)
5407–5413.
[10] A.C. Hiller, G.A. Grasa, M.S. Viciu, H.M. Lee, C. Yang, S.P. Nolan, J. Organomet.
Chem. 653 (2002) 69–82.
[11] A.J. Arduengo, R.L. Harlow, M. Kline, J. Am. Chem. Soc. 113 (1991) 361–363.
[12] R. Dorta, E.D. Stevens, N.M. Scott, C. Costabile, L. Cavallo, C.D. Hoff, S.P. Nolan, J.
Am. Chem. Soc. 127 (2005) 2485–2495.
ˇ
ˇ´
´ˇ
´
´
[27] T. Brıza, J. Kvıcala, P. Mysık, O. Paleta, J. Cermak, Synlett (2001) 685–687.
[28] A.J. Arduengo, R. Krafczyk, R. Schmutzler, Tetrahedron 55 (1999) 14523–14534.
[29] M.G. Gardiner, W.A. Herrmann, C.P. Reisinger, J. Schwarz, M. Spiegler, J. Organo-
met. Chem. 572 (1999) 239–247.
´ ˇ
´
´
´ˇ
´
ˇ
´ˇ
[30] O. Kysilka, M. Rybackova, M. Skalicky, M. Kvıcalova, J. Cvacka, J. Kvıcala, J. Fluorine
Chem. 130 (2009) 629–639.
´
[31] L.E. Kiss, I. Ko¨vesdi, J. Rabai, J. Fluorine Chem. 108 (2001) 95–109.
[32] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H.
Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev,
A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A.
Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C.
Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V.
Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A.
Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham,
C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen,
M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision D.01, Gaussian, Inc.,
Wallingford, CT, 2004.
[13] A.R. Chianese, X. Li, M.C. Janzen, J.W. Faller, R.H. Crabtree, Organometallics 22
(2003) 1663–1667.
[14] C.J. O’Brien, E.A.B. Kantchev, G.A. Chass, N. Hadei, A.C. Hopkinson, M.G. Organ, D.H.
Setiadi, T.-H. Tang, D.-C. Fang, Tetrahedron 61 (2005) 9723–9735.
[15] J.A. Gladysz, D.P. Curran, I.T. Horva´th (Eds.), Handbook of Fluorous Chemistry,
Wiley–VCH, Weinheim, 2004.
[33] C.J. O’Brien, E.A.B. Kantchev, C. Valente, N. Hadei, G.A. Chass, A. Lough, A.C.
Hopkinson, M.G. Organ, Chem.-Eur. J. 12 (2006) 4743–4748.
ˇ
´
´
´ˇ
´
ˇ
´ˇ
[16] O. Kysilka, M. Ryba´ckova, M. Skalicky, M. Kvıcalova, J. Cvacka, J. Kvıcala, Collect.
Czech. Chem. Commun. 73 (2008) 1799–1813.
[34] Crystallographic data for the structural analysis has been deposited with the
Cambridge Crystallographic Data Centre, CCDC No. 734053 for Compound 26.
Copies of this information may be obtained free of charge from the Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44 1223 336 033; E-mail:
deposit@ccdc.cam.ac.uk, or URL: http://www.ccdc.cam.ac.uk).
[17] L. Xu, W. Chen, J.F. Bickley, A. Steiner, J. Xiao, J. Organomet. Chem. 598 (2000) 409–
416.
[18] A. Fu¨rstner, L. Ackermann, B. Gabor, R. Goddard, C.W. Lehmann, R. Mynott, F.
Stelzer, O.R. Thiel, Chem. Eur. J. 7 (2001) 3236–3253.
[19] T.L. Merrigan, E.D. Bates, S.C. Dorman, J.H. Davies, Chem. Commun. (2000) 2051–
2052.
[35] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565.
[36] E.A.B. Kantchev, C.J. O’Brien, M.G. Organ, Aldrichim. Acta 39 (2006) 97–110.
[37] M.E. Mowery, P. DeShong, J. Org. Chem. 64 (1999) 3266–3270.
[38] Y. Fall, F. Berthiol, H. Doucet, M. Santelli, Synthesis (2007) 1683–1696.
ˇ
ˇ
ˇ´
´
[20] J. Kvı´cala, T. Brıza, O. Paleta, J. Cermak, Collect. Czech. Chem. Commun. 67 (2002)
1345–1358.
ˇ
ˇ´
´ˇ
´
[21] T. Brıza, J. Kvıcala, O. Paleta, J. Cermak, Tetrahedron 58 (2002) 3841–3846.