Synthesis, NMR spectroscopic characterisation and reactions of 2,6-difluorophenylxenon fluoride, 2,6-F2C6H3XeF

Article abstract of DOI:10.1016/j.jfluchem.2006.04.010

[2,6-F₂C₆H₃Xe][BF₄] is quantitatively transferred into 2,6-F₂C₆H₃XeF in reactions with [NMe₄]F. The latter has been isolated as a colourless solid which is stable in dichloromethane solution at room temperature for approximately 1 h. 2,6-F₂C₆H₃XeF readily reacts with Me₃SiX (X = Cl, Br, CN, NCO, OCOCF₃, OSO₂CF₃, C₆F₅, 2,6-F₂C₆H₃) to give compounds of general compositions 2,6-F₂C₆H₃XeX which were identified by multinuclear NMR experiments. Evidence was found for C₆H₅Xe(2,6-F₂C₆H₃) as a product of the reaction with C₆H₅SiF₃.

Full text of DOI:10.1016/j.jfluchem.2006.04.010

Journal of Fluorine Chemistry 127 (2006) 1440–1445
www.elsevier.com/locate/fluor
Synthesis, NMR spectroscopic characterisation and reactions
of 2,6-difluorophenylxenon fluoride, 2,6-F C H XeF
2
6 3
*
Harald Bock, Harald Scherer, Wieland Tyrra , Dieter Naumann
*
Institut f u¨ r Anorganische Chemie, Universit a¨ t zu K o¨ ln, D-50939 K o¨ ln, Germany
Received 13 April 2006; received in revised form 25 April 2006; accepted 25 April 2006
Available online 2 May 2006
ˇ
Dedicated to Professor Boris Zemva
Abstract
2,6-F C H Xe][BF ] is quantitatively transferred into 2,6-F C H XeF in reactions with [NMe ]F. The latter has been isolated as a colourless
[
2
6
3
4
2
6
3
4
solid which is stable in dichloromethane solution at room temperature for approximately 1 h. 2,6-F
Br, CN, NCO, OCOCF , OSO CF , C , 2,6-F ) to give compounds of general compositions 2,6-F
multinuclear NMR experiments. Evidence was found for C H Xe(2,6-F C H ) as a product of the reaction with C H SiF .
2
C
6
H
3
XeF readily reacts with Me
3
SiX (X = Cl,
3
2
3
6
F
5
2
C
6
H
3
2 6 3
C H XeX which were identified by
6
5
2
6
3
6
5
3
#
2006 Elsevier B.V. All rights reserved.
Keywords: Noble gas chemistry; Organoxenon compounds; NMR spectroscopy
1
. Introduction
exhibited to be those of highest thermal stability, e.g. [2,6-
F C H Xe][N(SO F) ] (T = 155 8C) [6]. With this knowl-
2
6
3
2
2
dec
Two reviews on the synthesis and reactions of organoxenon
edge, we decided to investigate possibilities to obtain further
derivatives with the 2,6-F C H Xe unit starting from 2,6-
derivatives have been recently published [1,2]. While ligand
exchange reactions with less or low co-ordinating anions have
been a major part of investigations [3–7], attempts to prepare
hypervalent [10-Xe-2] remained of lower success [8–12].
The first examples of organoxenon compounds with two
Xe–C bonds were those of Xe(C F ) [8–10] and Xe(C F )CN
2
6 3
F C H XeF and different silanes.
2 6 3
2. Results and discussion
6
5 2
6
5
2.1. Synthesis and characterisation of 2,6-
difluorophenylxenon fluoride, 2,6-F C H XeF
[
existence of 2,4,6-F C H XeC F and Xe(2,4,6-F C H ) by
9]. In a recent publication [12] Frohn and Theißen proved the
2
6 3
3
6
2
6
5
3 6 2 2
1
9
129
F and Xe NMR spectroscopic means and supported their
The sparingly soluble nature of [NMe ][BF ] in com-
4 4
results by theoretical calculations.
From all organoxenon compounds synthesised so far, those
bearing a 2,6-F C H moiety and a low co-ordinating anion
mon organic solvents makes [NMe ]F to a versatile tool for
4
ligand exchange reactions with arylxenon tetrafluoroborates
(Eq. (1)):
2
6 3
(
1)
The reaction proceeds selectively at ꢀ78 8C in CH Cl giving
2
2
2,6-F C H XeF in nearly quantitative yield. The colourless
2 6 3
*
Corresponding authors.
solid decomposes completely at ambient temperature within a
period of 30 min (dry Ar-atmosphere). In CH Cl solution a
E-mail addresses: tyrra@uni-koeln.de (W. Tyrra),
d.naumann@uni-koeln.de (D. Naumann).
2
2
0022-1139/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2006.04.010

H. Bock et al. / Journal of Fluorine Chemistry 127 (2006) 1440–1445
1441
half-life time of approximately 1 h can be estimated. The
decomposition proceeds with exclusive formation of 1,2,3-
trifluorobenzene as the only fluorine containing product
(
Eq. (2)):
(
3)
The reaction of 2,6-F C H XeF and C F I implies oxidation to
2
6
3
6 5
(2)
give an iodine(III) intermediate which decomposes in reactions
with the solvent mainly into 1,3-difluoro-2-iodobenzene, pen-
1
9
tafluorobenzene and 1,3-difluorobenzene (Eq. (4)). No
F
2,6-F C H XeF reacts with H O to give 1,3-difluorobenzene
probably in a manner as outlined for different arylxenon
NMR spectroscopic evidence is found for consecutive reactions
of the fluorine atom in these reactions:
2
6
3
2
(
4)
compounds [13]. At room temperature reactions with elemental
mercury, Hg(2,6-F C H )F (Eq. (3)) is presumably formed and
All in all, 2,6-F C H XeF shows the expected reaction beha-
2 6 3
viour as a strong oxidizing reagent.
NMR data of 2,6-F C H XeF are summarized in
2
6 3
identified in comparison with known data of related compounds
14]:
2
129
6 3
1
9
Table 1. All F and
[
Xe NMR values are in close
Table 1
Compilation of NMR data of 2,6-difluorophenylxenon compounds (d in ppm; J in Hz)
1
3
1
129 13
J( Xe, C)
19
d( F)
3
129 19
J( Xe, F)
129
d( Xe)
Compound
d( C)
d(C-2,6)
d(C-3,5)
d(C-4)
Solvent
T (8C)
a
[
[
(
(
(
(
(
(
(
(
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2,6-F
2
2
2
2
2
2
2
2
2
2
C
C
C
C
C
C
C
C
C
C
6
6
6
6
6
6
6
6
6
6
H
H
H
H
H
H
H
H
H
3
3
3
3
3
3
3
3
3
3
Xe][BF
4
]
88.8
89.4
99
156.8
157.5
159.0
159.5
157.3
157.0
162.7
157.3
115.2
115.5
113.4
116.3
114.2
112.3
111.2
114.2
112.2
136.5
136.7
137.8
138.4
134.8
137.4
134.9
137.3
130.7
134.9
131.6
140.1
141.1
ꢀ99.6
ꢀ100.1
ꢀ100.6
ꢀ103.6
ꢀ104.4
ꢀ101.4
ꢀ102.6
ꢀ102.3
ꢀ105.3
ꢀ129.5
ꢀ130.8
ꢀ102.3
ꢀ102.6
52
54
70
79
87
68
80
68
74
43
45
35
ꢀ2115
ꢀ2125
ꢀ2018
ꢀ2250
ꢀ2348
ꢀ2145
ꢀ2359
ꢀ2109
ꢀ2312
CD
CD
CD
CH
CD
CH
CH
CH
CD
CD
3
3
2
2
2
2
2
2
2
2
CN
CN
ꢀ30
+21
b,c
CF
3
Xe]OSO
)XeF
2
106
168
205
261
154
150
150
105
530
320
d
90.0
Cl
2
Cl
2
Cl
2
Cl
2
Cl
2
Cl
2
Cl
2
Cl
2
ꢀ70
ꢀ70
ꢀ80
ꢀ50
ꢀ70
e
)XeCl
104.1
103.7
91.6
f
)XeBr
g
)XeOCOCF
3
h
)XeCN
96.3
i
j
)XeNCO
96.0
ꢀ80
k
l
k
)XeC
)XeC
6
F
F
5
125.4
126.5
123.2
160.2
k
m
k
H
6
5
143.8
n
Xe(C
2,6-F
6
F
5
)
2
143.4
ꢀ2376
ꢀ2268
ꢀ2234
(CD
3
)
2
CO
ꢀ58
ꢀ70
ꢀ80
(
2
C
6
H
3
)
2
Xe
CH
CH
2
Cl
Cl
2
C
6
H
5
Xe(2,6-F
2
C
6
H
3
)
Broad
2
2
a
Taken from Ref. [22].
Taken from Ref. [5].
b
c
d
e
f
19
13
1
19 13
d(OSO
19
2
CF
3
): ꢀ78.5 ppm ( F); 121.3 ppm ( C), J( F, C) = 319 Hz.
1 129 19
d(Xe F): ꢀ8.4 ppm; J( Xe, F) = 3673 Hz.
The sample was contaminated by minor amounts of (CH
3
)
3
SiCl and (CH
3 3
) SiF.
3 3 3 3
The sample contained minor amounts of (CH ) SiBr and (CH ) SiF.
g
h
i
3 2
d(CF ): 116.9 ppm; d(CO ): 159.7 ppm.
d(CN): 127.4 ppm, broad. The sample was contaminated by minor amounts of (CH
d(NCO): 131.3 ppm.
3 3
) SiF.
j
Coupling is estimated, t1/2 ꢁ 60 Hz.
k
13 13
SiF. Data are collected from several C NMR experiments run at 193 and 203 K. 2D- C,
19
The sample was impured by traces of (CH
3
)
3
SiC
6
F
5
and (CH
3
)
3
F
2
19 13
HMBC NMR spectra were optimised for both ortho-fluorine resonances with the assumption of a J( F– C) coupling of 30 Hz. As a consequence of digital
resolution, shifts exhibit errors of up to ꢂ0.1 ppm, couplings of up to ꢂ5 Hz.
l
m
n
2
2
129
J( Xe– C): 29 Hz.
13
129
J( Xe– C): not observed.
13
2
Taken from Ref. [8]; J( Xe, C) = 148 Hz.
129
13

1442
H. Bock et al. / Journal of Fluorine Chemistry 127 (2006) 1440–1445
agreement with those reported for the related 2,4,6-
F C H XeF [12].
These findings are also in agreement with solid state
structures of [2,6-F C H Xe]OSO CF [17] and C F XeO-
COC F [18] indicating a significantly higher ionic character
3
6
2
2
6
3
2
3
6 5
6
5
for triflates than for perfluorocarboxylates. Differences are
13
C) NMR
2
Me SiX (X = Cl, Br, CN, NCO, OCOCF , OSO CF )
.2. Ligand exchange reactions of 2,6-F C H XeF and
2 6 3
1
best demonstrated comparing the J( Xe,
129
3
3
2
3
1
29
couplings and the Xe NMR shifts (Table 1). The differences
of the nature of xenon perfluoroalkanesulfonates and
perfluorocarboxylates have already been discussed earlier
All reactions of 2,6-F C H XeF and Me SiX proceed more or
2
6
3
3
less indiscriminately with formation of the corresponding
substitution products and Me SiF as the leaving moiety (Eq. (5)):
[
19].
3
(
5)
The selectivity of these reactions is best demonstrated with
the formation of 2,6-F C H XeBr, a compound which has
been expected to be unstable but now representing the first xenon
2.3. Syntheses of diarylxenon derivatives, 2,6-F C H XeAr
(Ar = C F , 2,6-F C H , C H )
2 6 3
2
6
3
6
5
2
6
3
6 5
bromine compound. In contrast, reactions with Me SiI exclu-
3
As recently described, bis(pentafluorophenyl)xenon,
Xe(C F ) , can either be generated via the reaction of XeF
2
sively gave 1-I-2,6-F C H , Me SiF and elemental xenon
2
6
3
3
6
5 2
(
Eq. (6)):
and Me SiC F in the presence of catalytic quantities of
3 6 5
(
6)
Chemicalshiftsandcouplingconstants(Table 1)intheseries2,6-
F C H XeF, 2,6-F C H XeCl and 2,6-F C H XeBr indicate
[NMe ]F [8,10] or the reaction of C F XeF and Cd(C F ) [9].
4 6 5 6 5 2
Cadmium reagents were also employed in the syntheses of
2,4,6-F C H XeC F and Xe(2,4,6-F C H ) [12].
2
6
3
2
6
3
2 6 3
increasing hypervalent character within the kernels C-Xe-Hal
Hal = F, Cl, Br)expressed by an increase of the absolutevalue of
3
6
2
6
5
3 6 2 2
(
the J( Xe, C) coupling constants together with a significant
In our investigations, we chose the silane route. Consider-
ably, reactions of 2,6-F C H XeF and Me SiAr (Ar = C F ,
1
129
13
2
6
3
3
6 5
1
29
highfield shift of the Xe NMR signal. All these findings are
supported by quantum-chemical calculations [15] and are in
agreement with data published elsewhere [12].
2,6-F C H ) proceeded selectively in the presence of catalytic
2 6 3
amounts of [NMe ]F to give the corresponding diarylxenon
4
compounds Xe(2,6-F C H ) and 2,6-F C H XeC F (Eq. (7)).
6 5
2
6
3 2
2
6
3
Reactions of 2,6-F C H XeF and Me SiCN, respectively
3
Unfortunately, none of the derivatives was obtained free of
impurities by the starting materials:
2
6
3
Me SiNCO, arise the compounds 2,6-F C H XeCN and 2,6-
2 6 3
3
(
7)
F C H XeNCO as most probable. In the case of the cyanide,
2 6 3
Due to differences in the polarity of the silicon–aryl bonds of
the starting materials Me SiAr, longer reaction times and
results match well with those given for C F XeCN [9], while
5
6
3
those obtained for 2,6-F C H XeNCO to our knowledge appear
2
higher temperatures were necessary for the 2,6-F C H
2 6 3
6
3
to be unique so far.
group transfer (24 h/ꢀ30 8C (2,6-F C H ) versus 1 h/
2
6 3
Great differences in thermal stability as well as NMR
spectroscopic data of the products resulting from exchange
reactions with Me SiOSO CF and Me SiOCOCF gave
ꢀ78 8C (C F )). The formation of the reactive silicate
6 5
intermediate appeared to be the rate determining step. It
has to be noted that formation of polyphenyls as described for
the decay of intermediately formed silicates [20] can be
excluded in reactions with Me SiC F under the chosen
3
2
3
3
3
materials of more ionic [5,16,17], [2,6-F C H Xe]OSO CF ,
3
2
6
3
2
or covalent character, 2,6-F C H XeOCOCF , with respect to
2
6
3
3
3
6 5
the xenon–oxygen bond [17,18] (Scheme 1).
conditions.

H. Bock et al. / Journal of Fluorine Chemistry 127 (2006) 1440–1445
1443
2 6 3 2 3
Scheme 1. Suggested bond structures for [2,6-F C H Xe]OSO CF and 2,6-
F
2
C
6
H
3
XeOCOCF
3
.
Scheme 2. Suggested bond structure for (2,6-F
2
C
6
H
3
6 5
)XeC F .
2,6-F C H XeC F was isolated as a pale yellow solid in
2 6 3 6 5
nearly quantitative yield with a decomposition point of
1
9
C H Xe(2,6-F C H ) was identified by F and
129
Xe NMR
6
5
2 6 3
approximately ꢀ20 8C. NMR spectra and chemical behaviour
spectroscopic means in comparison with related data
[8–10,12].
The characteristic multiplet of the 2,6-F C H group
1
9
make 2,6-F C H XeC F unambiguous (Table 1). F NMR
2
6
3
6 5
chemical shifts were detected in the region of those reported for
Xe(C F ) [8–10] and Xe(2,4,6-F C H ) [12], significantly
2
6 3
occurred 2 ppm deshielded from that of the starting material,
2,6-F C H XeF (ꢀ102.6 versus ꢀ100.6 ppm); additionally, the
6
5 2
3 6 2 2
shifted from those of salt-like fluorophenylxenon derivatives
e.g. [6,12,16,17]). The same can be applied in a somewhat less
significant manner with respect to 2,6-difluorophenylxenon
2
6 3
1
29
(
Xe NMR signal was shifted upfield by 216 ppm into the
region of values reported for other diarylxenon derivatives
(ꢀ2234 versus ꢀ2018 ppm) clearly indicating the formation of
C H Xe(2,6-F C H ).
1
29
compounds. The
matches well that of reported under comparable conditions [8–
Xe NMR chemical shift (ꢀ2312 ppm)
6
5
2 6 3
1
0,12]. While all shift values ( F, Xe, C) were found in the
9
129
13
1
expected regions, the J(Xe, C) couplings are outstanding. The
Similar changes were observed for Xe(2,6-F C H )
2 6 3 2
1
3
129
19
(Table 1). A close look onto the J( Xe, F) coupling
constant (35 Hz) in comparison with reported values [8–
10,12] exhibits that it could be interesting to determine
the relative sign of the coupling constants for a better
understanding of the nature of the 3c–4e-bonds in those
molecules.
1
absolute values of 105 Hz ( J(Xe, C) to 2,6-F C H ) and of
2
6 3
1
5
30 Hz ( J(Xe, C) to C F ) impressively differ from each other.
6 5
The sum of coupling constants – under the hypothesis of the
same relative sign – is nearly identical for both, 2,6-
F C H XeC F (635 Hz) and Xe(C F ) (640 Hz [8] or
2
6
3
6
5
6 5 2
6
be assumed for the compound, 2,6-F C H XeC F (Scheme 2).
30 Hz [9]), therefore, a strongly polarized 3c–4e bond must
Unfortunately, all three diarylxenon derivatives were found
to be too instable to be further investigated by diffraction
methods.
2
6
3
6 5
1
3
19
The C, F HMBC NMR spectrum clearly shows that 2,6-
F C H XeC F is a discrete molecule rather than a mixture of
2
6
3
6 5
1
9
symmetric diarylxenon compounds. The F signals of the 2,6-
F C H group correlate to the resonances of the quarternary
3. Experimental
2
6 3
carbon atoms of both, the 2,6-F C H group and the C F
6 5
3.1. General remarks
2
6
3
1
9
group. Additionally, F signals of the ortho-fluorine atoms of
the pentafluorophenyl ring show crosspeaks to the quarternary
carbon atoms. These correlations prove unambiguously that
both aromatic rings are bonded to the same xenon atom. Since
All chemicals were obtained from commercial providers
and used as received. XeF [21], [2,6-F C H Xe][BF ] [22],
Me Si(2,6-F C H ) [23] and Me SiC F [24] were prepared
2
2
6
3
4
3
2
6
3
3
6 5
1
3
the spectrum is recorded without C decoupling the two
2
crosspeaks owing to the larger J(C, F) coupling can be
4
distinguished from the two crosspeaks of the J(C, F) couplings
according to literature procedures. [NMe ]F was prepared from
4
[NMe ][BF ] and carefully dried KF in methanol.
4
4
Solvents were purified by standard methods [25]. Schlenk
(argon-atmosphere) and vacuum techniques were used through-
out all preparative procedures. NMR spectra were recorded on
by their larger splitting along the fluorine axis. As a
consequence, the resonances of the quarternary carbon atoms
can be assigned definitely. Furthermore, this spectrum allows to
identify all carbon signals of 2,6-F C H XeC F .
1
9
129
Bruker spectrometers: DRX 500 ( F, 470.8 MHz;
1
Xe,
138.3 MHz; C, 125.8 MHz), AMX 300 ( H, 300.1 MHz;
3
1
2
6
3
6 5
1
9
129
13
F, 282.4 MHz; Xe, 83.3 MHz; C, 75.5 MHz) and AC 200
All attempts to find at least NMR spectroscopic evidence for
C H Xe(2,6-F C H ) from reactions of 2,6-F C H XeF and
Me SiC H remained unsuccessful. This aim was achieved
1
19
13
6
5
2
6
3
2
6
3
( H, 200.1 MHz; F, 188.3 MHz; C, 50.3 MHz). Positive
shifts denote signals occurring downfield from the external
3
6 5
1
standards 1 M XeF in CH CN ( Xe), CCl F ( F) and Me Si
29
19
using C H SiF as an arylating reagent in fluoride mediated
6
5
3
2
3
3
4
1 13
( H, C).
reactions (Eq. (8)):
(
8)

1444
H. Bock et al. / Journal of Fluorine Chemistry 127 (2006) 1440–1445
3
.2. Synthesis of 2,6-difluorophenylxenon fluoride
CD Cl (15 mL) was condensed onto 0.45 g (1.36 mmol)
2,6-F C H Xe][BF ] and 0.13 g (1.40 mmol) [NMe ]F at
3.5.2. Reaction with Me Si(2,6-F C H )
3 2 6 3
The reaction was performed in a similar manner as described
for 2,6-F C H XeC F with 0.21 g (0.78 mmol) 2,6-
2
2
2
6
3
6 5
[
F C H XeF, 0.15 g (0.78 mmol) Me Si(2,6-F C H ) and a
2 6 3 3 2 6 3
2
6
3
4
4
ꢀ
100 8C. The temperature was raised to ꢀ78 8C and the
catalytic amount of [NMe ]F. Complete exchange was achieved
4
suspension stirred for 2 h. During this period, [NMe ][BF ]
4
after 24 h of stirring a CD Cl (10 mL) solution at ꢀ30 8C.
4
2
2
quantitatively precipitated and was removed by filtration at
78 8C. 2,6-F C H XeF was analysed by NMR spectroscopy
Attempted isolation by condensing off all volatiles at ꢀ40 8C
ꢀ
led to decomposition of Xe(2,6-F C H ) mainly into
2 6 3 2
2
6
3
0
0
(
cf. Table 1). The pure compound was obtained after distilling
elemental xenon and 2,2 ,6,6 -tetrafluorobiphenyl.
off all volatile material at ꢀ40 8C. 2,6-F C H XeF was
2
6 3
obtained as a colourless solid in nearly quantitative yield
0.35 g, 1.33 mmol, 98%).
(
3.5.3. Reaction with C H SiF
3
6
5
Quantities of 0.25 g (1.54 mmol) C H SiF and 0.28 g
6
5
3
(
3.00 mmol) [NMe ]F were stirred in 10 mL CH Cl for 1 h
4 2 2
3.3. Reactions of 2,6-difluorophenylxenon fluoride with
water, mercury and pentafluoroiodobenzene
at 0 8C. The mixture was cooled to ꢀ90 8C and 0.20 g
(
0.76 mmol) 2,6-F C H XeF were added. After stirring for
2 6 3
20 min at this temperature a white solid had precipitated. The
To solutions of 0.07 g (0.26 mmol) 2,6-F C H XeF in 3 mL
6 3
2
reaction was terminated and the solution investigated by NMR
spectroscopic methods. Isolation was not attempted.
CH Cl at ꢀ50 8C 0.10 g (5.55 mmol) H O, 0.10 g
2
2
2
(0.50 mmol) Hg, 0.12 g (0.26 mmol) C F I, respectively, were
6 5
added. Reaction mixtures were allowed to warm to room
1
9
Acknowledgement
temperature over a period of 1 h and analysed by F NMR
spectroscopy. With water, exclusive formation of 1,3-F C F
6 4
2
Financial support by the Fonds der Chemischen Industrie is
gratefully acknowledged.
was observed which was complete after 12 h. The reaction with
elemental mercury proceeded selectively to give one mercury
1
9
3
derivative (d( F) ꢀ91.6 ppm; J(HgF) 489 Hz) which might be
References
assigned to Hg(2,6-F C H )F. In the reaction with C F I, 1,3-
6 5
2
6
3
F -2-I-C H , 1,3-F C H and C F H were formed.
2
6
3
2
6
4
6 5
[
[
1] H.-J. Frohn, V.V. Bardin, Organometallics 20 (2001) 4750.
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.4. Reactions of 2,6-difluorophenylxenon fluoride with
trimethylsilicon derivatives, Me SiX (X = Cl, Br, CN, NCO,
3
[
[
[
3] H.-J. Frohn, Nachr. Chem. Tech. Lab. 41 (1993) 956.
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OCOCF , OSO CF )
3
2
3
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To solutions of 0.07 g (0.26 mmol) 2,6-F C H XeF in 3 mL
2 6 3
CD Cl 0.28 mmol Me SiX were added via a syringe at
2
[6] Yu.L. Yagupolskii, W. Tyrra, R. Gnann, N. Maggiarosa, D. Naumann, J.
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2
3
ꢀ
78 8C. Immediately after addition of the silicon compound,
F NMR spectra were recorded proving the formation of
1
9
[7] H.-J. Frohn, T. Schroer, G. Henkel, Angew. Chem. 111 (1999) 2751;
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3
2
554.
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[
[
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4
588.
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3
6 5
F C H , C H )
2
[10] H. Bock, D. Hinz-H u¨ bner, U. Ruschewitz, D. Naumann, Angew. Chem.
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6
3
6 5
1
H. Bock, D. Hinz-H u¨ bner, U. Ruschewitz, D. Naumann, Angew. Chem.
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3
.5.1. Reaction with Me SiC F
3 6 5
To a solution of 0.07 g (0.26 mmol) (2,6-F C H )XeF in
2
6
3
[11] H. Schmidt, H. Scherer, W. Tyrra, J. Hahn, D. Naumann, Inorg. Chem. 43
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3
quantity of [NMe ]F were added. The reaction mixture was
mL CD Cl , 0.03 g (0.28 mmol) Me SiC F and a very small
2 2 3 6 5
[
[
[
12] H.-J. Frohn, M. Theißen, J. Fluorine Chem. 125 (2004) 981.
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4
stirred for 1 h at ꢀ78 8C. The completeness of the exchange
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2
1601.
[15] H. Bock, Dissertation, K o¨ ln, 2003.
,6-F C H XeC F was isolated as a pale yellow solid in
2 6 3 6 5
nearly quantitative yield after removal of all volatile material in
high vacuum at ꢀ40 8C. In the solid state in a dry argon
atmosphere, it decomposes at approximately ꢀ20 8C. Caution!
All attempts to manipulate solid 2,6-F C H XeC F with glass
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[
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2
6
3
6 5
[
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99.
or metal spatula led to direct explosions even at ꢀ78 8C or
below.

H. Bock et al. / Journal of Fluorine Chemistry 127 (2006) 1440–1445
1445
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