A first methodical approach to salts with unsymmetrical fluorophenyl(pentafluorophenyl)difluoroiodonium(V) cations [Rf(R F)IF2]+ (Rf=x-FC6H 4, x=2, 3, 4; RF=C6F5)

Article abstract of DOI:10.1016/j.tet.2010.04.047

A promising approach to the unknown type of [Ar′(Ar)IF₂]X salts is offered. x-FC₆H₄IF₄ (x=2, 3, 4) reacts with C₆F₅BF₂ in CH₂Cl₂ and forms [x-FC₆H₄(C₆F₅)IF ₂][BF₄] salts in good yields. For [4-FC₆H ₄(C₆F₅)IF₂][BF₄] the fluoro-oxidizer property is shown in reactions with weakly reducing agents like E(C₆F₅)₃ (E=P, As, Sb, Bi) and ArI (Ar=4-FC₆H₄, C₆F₅). The fluorine/aryl substitution method is also applied to the synthesis of [(4-FC₆H₄)₂IF₂][BF₄], an example with two identical aryl groups in the difluoroiodonium(V) moiety.

Full text of DOI:10.1016/j.tet.2010.04.047

Tetrahedron 66 (2010) 5762e5767
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A first methodical approach to salts with unsymmetrical fluorophenyl
(pentafluorophenyl)difluoroiodonium(V) cations [Rf(RF)IF2]þ (Rf¼x-FC6H4, x¼2, 3,
4; RF¼C6F5)
,
a
b
Hermann-Josef Frohn a , André Wenda , Ulrich Florke
*
€
a Inorganic Chemistry, University of Duisburg-Essen, Lotharstr. 1, 47048 Duisburg, Germany
b Inorganic and Analytical Chemistry, University of Paderborn, Warburgerstr. 100, 33098 Paderborn, Germany
a r t i c l e i n f o
a b s t r a c t
A promising approach to the unknown type of [Ar0(Ar)IF2]X salts is offered. x-FC6H4IF4 (x¼2, 3, 4) reacts
with C6F5BF2 in CH2Cl2 and forms [x-FC6H4(C6F5)IF2][BF4] salts in good yields. For [4-FC6H4(C6F5)IF2][BF4]
the fluoro-oxidizer property is shown in reactions with weakly reducing agents like E(C6F5)3 (E¼P, As, Sb,
Bi) and ArI (Ar¼4-FC6H4, C6F5). The fluorine/aryl substitution method is also applied to the synthesis of
[(4-FC6H4)2IF2][BF4], an example with two identical aryl groups in the difluoroiodonium(V) moiety.
Ó 2010 Elsevier Ltd. All rights reserved.
Article history:
Received 19 March 2010
Accepted 12 April 2010
Available online 5 May 2010
Keywords:
Iodonium(V) salts
Aryliodine(V) tetrafluorides
Arylboron difluorides
Fluoro-oxidizers
1. Introduction
The nature of [(C6H5)2IF2]F was elucidated first in 2004 by
Hoyer.5 She was able to get the single crystal structure and could
The chemistry of organoderivatives of iodine(V) is far less
developed than that of iodine(III). While di(aryl)iodonium salts1
represent the largest number of polyvalent organoiodine(III)
compounds, only few examples of the corresponding di(aryl)
iodonium(V) salts are known. This is astonishing because Mas-
son2 published a fundamental access to this type of compounds
already in 1935. He obtained [(C6H5)2IO]OH by ‘self-condensation’
of C6H5IO2 in the presence of NaOHaq (Eq. 1).
prove that no (C6H5)2IF3 was present. Three [(C6H5)2IF2]þ cations
ꢀ
are bridged by fluoride ions in distances of 2.5e2.6 A. Each
[(C6H5)2IF2]þ cation has in agreement with the VSEPR notation
(AB2C2E) a j-trigonal bipyramidal geometry.
Up to now all approaches to salts with cations of the general
type [(Ar)2IY2]X were principally based on the ‘self-condensation’
step by Masson and allowed only symmetrical di(aryl) constitu-
tions. In addition it is worth to mention that Masson’s method
cannot be applied when a larger number of electron-withdrawing
substituents like F or NO2 are present in the aryl group. In such
cases the aryl group is eliminated under basic conditions (forma-
tion of AreH).6 In 2008 we have published a new methodical ap-
proach. We obtained the symmetrical example, [(C6F5)2IF2][BF4], by
F/C6F5 substitution in C6F5IF4 with C6F5BF2.7 In the present paper
we show the potential of this approach for the synthesis of un-
symmetrical [Rf(RF)IF2][BF4] salts. Furthermore we want to show
that [Ar(Ar0)IF2]þ cations are good fluoro-oxidizers. This property
may be useful in future to introduce fluorine into an organic moiety.
L
2C6H5IO2DOHL/½ðC6H5Þ2IOꢀOHD½IO3ꢀ
(1)
Beringer3 used this reaction in 1968 to obtain the first examples
of [(Ar)2IO]X salts by metathesis (Eq. 2).
I
Â
Ã
Â
Ã
Â
Ã
ðArÞ2IO OH HOAc ðArÞ IO OAcF
ðArÞ IO X
(2)
M X
F
ƒƒ!
ƒ!
2
2
Ar¼C6H5, 4-FC6H4, 4-MeC6H4; MI¼Na, K; X¼F, Cl, Br.
Based on this results, in 1972 Yagupol’skii4 published the syn-
theses of the first di(aryl)difluoroiodonium(V) salts (Eq. 3).
Â
Ã
Â
Ã
Â
Ã
SF4
SF4
2. Experimental results
ðArÞ IO OAcF
ðArÞ IF2 OAcF
ðArÞ2IF2
F
(3)
ƒ!
ƒ!
2
2
x-FC6H4IF4 (x¼2, 3, 4) reacted with C6F5BF2 in weakly
coordinating solvents like CH2Cl2 under F/C6F5 substitution and the
products [x-FC6H4(C6F5)IF2][BF4] precipitated and could be easily
isolated in good yields (Eq. 4).
Ar¼C6H5, 4-FC6H4.
* Corresponding author. E-mail address: h-j.frohn@uni-due.de (H.-J. Frohn).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.04.047

H.-J. Frohn et al. / Tetrahedron 66 (2010) 5762e5767
5763
form the iodonium(V) tetrafluoroborate, stabilized by lattice energy
(Scheme 1).
CH2Cl2
x ꢁ FC6H4IF4 þ C6F5BF2
½x ꢁ FC H ðC F ÞIF ꢀ½BF ꢀY
ƒƒƒƒƒƒ!
6
4
6
5
2
4
ꢂ20 ꢃC=ꢂ3 h
(4)
ArBF
Ar’IF
Ar’IF -F--BF Ar
A
<Ar’(Ar)IF + BF >
B
[Ar’(Ar)IF ][BF ]
C
It is important to mention that few percent of [x-FC6H4(C6F5)I]
[BF4] were often included in the product. The different channels,
which explain the reduction of [x-FC6H4(C6F5)IF2][BF4] are dis-
cussed in Ref. 7.
Scheme 1.
The pair of starting materials with opposite functionalities can
alsobeused, aswasdemonstrated for[4-FC6H4(C6F5)IF2][BF4] (Eq. 5).
C6F5BF2 is a stronger Lewis acid than 4-FC6H4BF2 and BF3, based
on the result of gas phase fluoride affinity calculations.12 Thus the
polarization of an IeF bond of the IF4 group (A in Scheme 1) pro-
ceeded better with C6F5BF2 (Eq. 4) than with 4-FC6H4BF2 (Eq. 5).
Furthermore the IeF bond in 4-FC6H4IF4 (Eq. 4) can be more easily
polarized than in C6F5IF4 (Eq. 5). Additionally, the nucleofugality of
the C6F5 group (Ar in species A, Scheme 1) is higher than that of the
4-FC6H4 group. All three arguments explain the higher reaction rate
of Eq. 4 in relation to Eq. 5. We have found that in the reaction of
C6F5IF4 (strong IeF bond) with 4-FC6H4BF2 (weak fluoride acceptor)
(Eq. 5) the quantity of the by-product [4-FC6H4(C6F5)I][BF4] was of
the same magnitude as [4-FC6H4(C6F5)IF2][BF4]. This result is in
agreement with more frequent attacks of the strong Lewis acid on
chlorine in the solvent CH2Cl2 during the slow reaction. Chloride is
an effective reducing agent for [(Ar)2IF2]þ cations.7
CH2Cl2
C6F5IF4 þ 4 ꢁ FX6H4BF2
½4 ꢁ FC H ðC F ÞIF ꢀ½BF ꢀY
ƒƒƒƒƒƒ!
6
4
6
5
2
4
ꢂ20 ꢃC=ꢄ4 d
(5)
But the reaction proceeded significantly slower and was ac-
companied by a large amount of reduced product [4-FC6H4(C6F5)I]
[BF4] (molar ratio [4-FC6H4(C6F5)IF2][BF4]/[4-FC6H4(C6F5)I][BF4]/
C6F5I¼52:46:3).
In order to evaluate the influence of a low number of fluorine
substituents in the aryl group of ArIF4 and ArBF2 on the reaction
rate, we have additionally studied the reaction of 4-C6H4IF4 and
4-FC6H4BF2 (Eq. 6).
Â
Ã
CH2Cl2
All [x-FC6H4(C6F5)IF2][BF4] salts were isolated as colorless solids
in good yields. We were able to get single crystals of [4-FC6H4(C6F5)
IF2][BF4] directly from the reaction mixture and to determine the
molecular structure. [4-FC6H4(C6F5)IF2][BF4] crystallizes in the
4 ꢁ C6H4IF4 þ 4 ꢁ FC6H4BF2
ð4 ꢁ FC6H4Þ2IF2 ½BF4ꢀY
ƒƒƒƒƒƒ!
20 ꢃC=<3 h
(6)
All three [x-FC6H4(C6F5)IF2][BF4] salts are colorless solids and
decompose exothermically without proceeding melting. The
hypervalent IF2 triad in combination with the high partial positive
charge on iodine make these salts attractive as fluoro-oxidizers. We
tested this property in reactions of [4-FC6H4(C6F5)IF2][BF4] with
weakly reducing E(C6F5)3 compounds (E¼P, As, Sb) (Eq. 7). In case of
E¼Bi, side-reactions became dominant (see Discussion).
ꢀ
ꢀ
monoclinic space group P21/n (a¼13.4487(16) A, b¼12.2497(15) A,
ꢀ
c¼19.390(2) A,
a
¼90ꢃ,
b
¼94.056(2)ꢃ,
g
¼90ꢃ) with Z¼8 and two
symmetry independent cations and anions in the asymmetric unit.
The cation has a
j-trigonal bipyramidal geometry with both hyper-
valently bonded fluorine atoms in the axial positions (Fig. 1). Both
ꢀ
ꢀ
CeI (averaged 2.09(3) A) and FeI distances (averaged 1.92(2) A) are
longer thanin the[(C6F5)2IF2]þ cation (averaged 2.064(5) A and 1.913
(3) A, respectively), mainly caused by smaller electrostatic contri-
ꢀ
ꢀ
MeCN
½4 ꢁ FC6H4ðC6F5ÞIF2ꢀ½BF4ꢀ þ EðC6F5Þ3
ƒƒƒ!
butions in the bonds. For the same reason the IeC6F5 distance is
shorter than the IeC6H4F distance. In [4-FC6H4(C6F5)IF2][BF4] the
averaged FeIeF angle is slightly increased and the CeIeC angle
decreased relative to the [(C6F5)2IF2]þ cation.7 The latter phenomena
can be deduced to the larger demand of space of C6F5 groups.
20 ꢃC
½4 ꢁ FC6H4ðC6H5ÞIꢀ½BF4ꢀ þ ðC6H5Þ3EF2
E¼P, As, Sb.
(7)
The aryl iodides C6F5I and 4-FC6H4I were chosen to demon-
strate the electronic influence of aryl groups with strongly dif-
fering electron-withdrawing character on the reaction rate with
[4-FC6H4(C6F5)IF2][BF4] (Eq. 8).
MeCN
20 ꢃC
½4 ꢁ FC H ðC F ÞIF ꢀ½BF ꢀ þ ArI
ƒƒƒ!
6
4
6
5
2
4
½4 ꢁ FC6H4ðC6H5ÞIꢀ½BF4ꢀ þ ArIF2
Ar¼C6F5I, 4-FC6H4I.
(8)
3. Discussion
The interaction of hypervalent elementefluoride moieties with
fluoroorganyldifluoroboranes is a widely applicable method for F/R
substitution. It was well elaborated for aryl-, alkenyl-, and alky-
nylxenonium8 and diorganyliodonium(III) salts.9,10 The hypervalent
bond in Ar0IF4 compounds is characterized by significant partial
negative charges on fluorine (>ꢁ0.5) and strong partial positive
charges on iodine(V) (<3.0).11 As a consequence of interaction of
the Lewis acidic aryldifluoroborane with aryliodine tetrafluoride
the borane takes over partially borate character and the nucleo-
philic property of its aryl group increases. Parallel the iodine center
becomes more electrophilic. The transition state allows the transfer
of the aryl group to iodine(V) and of fluorine to boron and ends
with two kinetically independent species: Ar0(Ar)IF3 and BF3, which
Figure 1. Molecular structure of the [4-FC6H4(C6F5)IF2]þ cation: selected distances/A
ꢀ
and angles/ꢃ: I1eC101 2.072(7), I1eC107 2.113(7), I1eF101 1.919(4), I1eF102 1.932(5),
C101eI1eC107 99.6(3), F101eI1eF102 167.24(19).
ꢀ
There are three significant IeF contacts (2.787(5)e2.843(6) A)
between two weakly coordinating [BF4]ꢁ anions and iodine(V) of
the electrophilic cation (Fig. 2): one trans to the 4-FC6H4 group and
two in a chelating manner trans to the C6F5 group. These contacts
13
ꢀ
are w18% shorter than the sum of van der Waals radii of 3.45 A.

5764
H.-J. Frohn et al. / Tetrahedron 66 (2010) 5762e5767
F3,5 reflects preferentially the inductive effect of the iodine center
whereas the shift value of F4 informs about the polarization of the
0
0
aryl
p
-system. In the x-FC6H4 group F3 and F4 are significantly
deshielded with respect to the monovalent x-FC6H4I parent com-
0
pounds. Generally, the shift value F2 is strongly influenced by steric
aspects of the iodine environment. We have observed a worth to
mention deshielding of the fluorine atoms of [BF4]ꢁ from
[(C6F5)2IF2]þ via [2- and 3-/4-FC6H4(C6F5)IF2]þ to [(4-FC6H4)2]þ.
Table 1
Characteristic 19F NMR shift valuesa
d
/ppm of [x-FC6H4(C6F5)IF2][BF4] (x¼2, 3, 4) and
related salts [(4-FC6H4)2IF2][BF4] and [(C6F5)2IF2][BF4] in MeCN at 24 ꢃ
C
Compound
IF2
F2,6
F3,5
F4
x-FC6H4 [BF4]ꢁ
ꢁ98.9 ꢁ147.3
[2-FC6H4(C6F5)IF2][BF4]b ꢁ66.6 ꢁ125.8 ꢁ154.7 ꢁ137.6
[3-FC6H4(C6F5)IF2][BF4]c ꢁ74.2 ꢁ127.0 ꢁ155.4 ꢁ138.5 ꢁ103.1 ꢁ146.1
[4-FC6H4(C6F5)IF2][BF4]d ꢁ74.0 ꢁ127.4 ꢁ155.5 ꢁ138.7
ꢁ99.6 ꢁ146.3
ꢁ100.5 ꢁ145.9
[(4-FC6H4)2IF2][BF4]
[(C6F5)2IF2][BF4]e
ꢁ85.3
d
d
d
ꢁ58.2 ꢁ125.4 ꢁ153.7 ꢁ136.3
d
ꢁ147.7
a
For nJ-coupling constants, see Experimental part.
b
c
2-FC6H4I and 2-FC6H4IF2 d/ppm: ꢁ93.4 and ꢁ97.6, ꢁ163.8 (IF2).
3-FC6H4I and 3-FC6H4IF2 d/ppm: ꢁ110.3 and ꢁ108.1, ꢁ173.0 (IF2).
d
e
4-FC6H4I and 4-FC6H4IF2
C6F5I and C6F5IF2
d
/ppm: ꢁ114.2 and ꢁ107.9, ꢁ171.1 (IF2).
d
/ppm: ꢁ120.2, ꢁ160.4, ꢁ153.6 and ꢁ122.9, ꢁ157.0, ꢁ144.5,
ꢁ160.6 (IF2).
Figure 2. Cationeanion contacts in [4-FC6H4(C6F5)IF2][BF4].
The carbon atom C1 of the C6F5 group in [x-FC6H4(C6F5)IF2]þ is
slightly more deshielded than in [(C6F5)IF2]þ (Tables 2). Both car-
0
bon atoms C1 and C1 of each [x-FC6H4(C6F5)IF2]þ cation are
deshielded by 41.2e45.1 ppm with respect to x-FC6H4I or C6F5I,
respectively.
All three [x-FC6H4(C6F5)IF2][BF4] salts can be stored at ambient
temperature under an dry atmosphere without decomposition. DSC
informed that decomposition proceeded without proceeding
melting in the series [3-FC6H4(C6F5)IF2][BF4] (134.3 ꢃC)<[4-
FC6H4(C6F5)IF2][BF4] (142.6 ꢃC)<[2-FC6H4(C6F5)IF2][BF4] (197.4 ꢃC)
according to their Tonset data.
The Raman data were assigned by comparison with the parent
compounds x-FC6H4I and C6F5I and based on DFT-calculations
(B3LYP/cc-pVTZ-PP). The characteristic symmetrical IF2 vibration in
[x-FC6H4(C6F5)IF2][BF4] salts gave rise to intensive Raman bands at
556 (x¼2), 554 (x¼3), and 542 cmꢁ1 (x¼4). The IF2 deformation
mode appeared at 175 (n¼2), 154 (n¼3), and 163 cmꢁ1 (n¼4) in the
same region as it was found for C6F5IF2 (174 cmꢁ1).14
[x-FC6H4(C6F5)IF2][BF4] salts are well soluble in MeCN. In such
solutions we can assume a competition between the neutral base
MeCN and the anion to coordinate at iodine(V). The NMR data in-
form of this process. In the 19F NMR (Table 1) the shielding trend of
the IF2 group from x¼2 to 4 and the highest shielding in [(4-
FC6H4)2IF2][BF4] and the lowest in [(C6F5)2IF2][BF4] are in agree-
ment with the inductive effect of the involved aryl groups and
correlate with the individual partial charge on iodine(V). A high
partial positive charge on iodine polarizes not only the attached
fluorine atoms but also both aryl groups. The C6F5 group is a good
probe to inform about such a polarization process. The shift value of
Finally, the fluoro-oxidizer property of [4-FC6H4(C6F5)IF2][BF4]
in reactions with an excess of E(C6F5)3 (E¼P, As, Sb, Bi) (Eq. 7)
and C6F5I or 4-FC6H4I (Eq. 8) in MeCN will be discussed. The
addition of two fluorine atoms to E(C6F5)3 under total con-
sumption of [4-FC6H4(C6F5)IF2][BF4] proceeded comparatively fast
for E¼As (3.5 h) and Sb (0.5 h), whereas the long reaction times
for E¼P and Bi were accompanied by consecutive reactions. In
case of E¼P approx. one-third of (C6F5)3PF2 was hydrolyzed by
water vapor, which penetrates through the thin FEP-wall of the
trap. In case of E¼Bi(C6F5)3 no (C6F5)3BiF2 was observed and
[4-FC6H4(C6F5)I][BF4] was only a minor product besides the major
C6F5H, [(C6F5)2I][BF4], and 1,4-F2C6H4. The latter two can be
explained by elimination of
a higher pentafluorophenylated
iodonium(V) species like [4-FC6H4(C6F5)2IF][BF4]. The F/C6F5
substitution in IF5 by Bi(C6F5)3 is well known.11 It is important to
mention that all reactions of [(C6F5)2IF2][BF4] with E(C6F5)3 pro-
ceeded significant faster than with [4-FC6H4(C6F5)IF2][BF4] and
differing with Bi(C6F5)3 the desired product (C6F5)3BiF2 was
obtained.7 [4-FC6H4(C6F5)IF2][BF4] reacted with 4-FC6H4I and
C6F5I under fluorine addition (Eq. 8). The reaction with 4-FC6H4I
proceeded approx. four times faster than with C6F5I, where 11
d were needed for the total consumption of [4-FC6H4(C6F5)IF2]
[BF4].
Table 2
Characteristic 13C NMR shift valuesa
d
/ppm of [x-FC6H4(C6F5)IF2][BF4] (x¼2, 3, 4) and related salts [(4-FC6H4)2IF2][BF4] and [(C6F5)2IF2][BF4] in MeCN at 24 ꢃ
C
Compound
C6F5 group
C1
x-FC6H4 group
0
0
0
0
0
0
C2,6
C3,5
C4
C1
C2
C3
C4
C5
C6
[2-FC6H4(C6F5)IF2][BF4]
[3-FC6H4(C6F5)IF2][BF4]
[4-FC6H4(C6F5)IF2][BF4]
[(4-FC6H4)2IF2][BF4]
[(C6F5)2IF2][BF4]
113.5
114.0
114.1
d
147.0
146.8
146.9
d
140.0
139.4
139.6
d
148.5
147.9
148.0
d
125.7
135.8
129.1
133.4
d
159.6
118.6
134.4
133.2
d
120.8
164.4
121.4
120.9
d
129.4
124.5
167.8
167.3
d
132.2
134.6
121.4
120.9
d
140.5
127.4
134.4
133.2
d
112.8
146.9
140.0
148.8
a
For nJ-coupling constants, see Experimental part.

H.-J. Frohn et al. / Tetrahedron 66 (2010) 5762e5767
5765
4. Conclusion
(m, 2-FC6H4, 1F); e125.8 (br, Dn ¼55 Hz, o-C6F5, 2F); ꢁ137.6 (ttt, 3J
½
(F4,F3,5)¼21 Hz, 4J(F4,F2,6)¼9 Hz, 6J(F4,F(IF))¼2 Hz, p-C6F5,1F); ꢁ154.7
The Lewis acid assisted substitution of a hypervalently bonded
fluorine atom by an aryl group can be applied to aryliodine(V)
tetrafluorides and delivers [Ar0(Ar)IF2][BF4] iodonium(V) salts with
a cation of high electrophilicity. The electrophilic nature of the
cation can be deduced from cationeanion interactions in the solid
state and from 19F NMR data in MeCN for solutions. This type of
salts opens a new application for polyvalent iodine compounds,
namely to act as a fluoro-oxidizer. Di(aryl)difluoroiodonium(V)
salts as well with a symmetrical as with a unsymmetrical consti-
tution concerning both aryl groups are accessible by the reaction of
ArIF4 and ArBF2 in weakly coordinating solvents. There are
reasonable arguments that the reported method for di(aryl)
difluoroiodonium salts can be even transferred to alkynyl- and
alkenyl-iodonium compounds.
(m, m-C6F5, 2F); [2-FC6H4(C6F5)I][BF4]
d
: ꢁ94.7 (m, 2-FC6H4, 1F);
ꢁ121.1 (m, o-C6F5, 2F); ꢁ142.2 (tt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼6 Hz,
p-C6F5, 1F); ꢁ155.8 (m, m-C6F5, 2F); [BF4]ꢁ
d
:¼ꢁ147.3 (s, BF4, 4F).
0
0
1H NMR (CH3CN, 24 ꢃC) [2-FC6H4(C6F5)IF2]þ
d
: 8.2 (m, H5 , 1H);
0
0
8.0 (m, H6 , 1H);0 7.8 (mo, H4 , 1H); 7.8 (mo, H3 , 1H); [2-FC6H4(C6F5)
0
0
0
I]þ : 8.3 (m, H5 , 1H); 7.8 (m, H6 , 1H); 7.5 (m, H3 , 1H); 7.4 (m, H4 ,
d
1H); CH2Cl2 d: 5.4 (s); molar ratio [(2-FC6H4)2IF2]þþ[(2-FC6H4)2I]þ/
CH2Cl2¼100:12.
0
13C NMR (CH3CN, 24 ꢃC) [2-FC6H4(C6F5)IF2]þ d: 159.6 (dm, 1J(C2 ,
0
0
F2 )¼261 Hz, 2-FC6H4, C2 ), 148.5 (dm, 1J(C4,F4)¼265 Hz, C6F5, C4);
0
147.0 (dm, 1J(C2,F2)¼1J(C6,F6)¼261 Hz, C6F5, C2,6); 140.5 (dmo, 1J(C6 ,
0
0
H6 )¼175 Hz, 2-FC6H4, C6 ); 140.0 (dmo, 1J(C3,F3)¼1J(C5,F5)¼253 Hz,
0
0
0
C6F5, C3,5); 132.2 (dm, 1J(C5 ,H5 )¼173 Hz, 2-FC6H4, C5 ); 129.4 (dm, 1J
0
0
0
0
(C4 ,H4 )¼171 Hz, 2-FC6H4, C4 ); 125.7 (m, 2-FC6H4, C1 ); 120.8 (dm,
0
0
0
1J(C3 ,H3 )¼174 Hz, 2-FC6H4, C3 ); 113.5 (m, C6F5, C1).
11B NMR (CH3CN, 24 ꢃC) [BF4]ꢁ d: ꢁ1.3 (s, BF4).
5. Experimental part
5.1. General
Raman (20 ꢃC)
n
: 83 (81), 136 (35), 159 (21), 175 (25), 194 (33),
210 (20), 220 (22), 244 (18), 271 (23), 353 (11), 363 (10), 374
(15), 383 (17), 441 (19), 463 (13), 494 (28), 532 (21), 556 (100),
587 (23), 617 (5), 638 (16), 680 (4), 703 (4), 762 (15), 803 (4),
823 (17), 1005 (13), 1041 (14), 1106 (4), 1134 (5), 1167 (6), 1237
(8), 1271 (6), 1297 (5), 1408 (5), 1497 (4), 1522 (3), 1575 (8), 1593
All moisture sensitive compounds were handled under an
atmosphere of dry argon. Reactions were carried out in vessels
constructed from FEP tubes (o.d.¼4.1 mm, i.d.¼3.5 mm or o.
d.¼9.0 mm, i.d¼8.0 mm, FEP is a co-polymer of (CF2CF2)n and (CF2C
(CF3)F)m). Acetonitrile was refluxed and distilled from KMnO4 and
repeatedly refluxed and distilled from P4O10. Dichloromethane was
treated in sequence with concd H2SO4, Na2CO3(aq), and H2O and fi-
nally refluxed and distilled from P4O10. NMR spectra were recorded
on a Bruker spectrometer AVANCE 300 (13C at 75.47 MHz, 11B at
96.29 MHz, 19F at 282.40 MHz), and 1H at 300.13 MHz. The chemical
shifts were referenced to BF3$OEt2/CDCl3 15% v/v (11B), TMS (13C,1H),
(4), 1636 (9) cmꢁ1
.
5.3. [3-FC6H4(C6F5)IF2][BF4]
A ꢁ78 ꢃC cold solution of C6F5BF2 (0.85 mmol) in CH2Cl2 (1.2 mL)
was added under stirring to a ꢁ40 ꢃC cold solution of 3-FC6H4IF4
(281 mg, 0.94 mmol) in CH2Cl2 (3 mL). Within 2 h the solution was
warmed to 2 ꢃC and formed a slightly yellow suspension. The solid
was separated and washed with CH2Cl2 (3 mL) and pumped in
vacuum at 20 ꢃC to yield 305 mg, 0.0555 mmol, 61%. From 1H NMR
resulted that 0.42 CH2Cl2 are co-crystallized per [3-FC6H4(C6F5)IF2]
[BF4].
and CCl3F (19F) (C6F6 as a secondary reference,
d
¼ꢁ162.9 ppm). Shift
values of overlapping signals are marked by o. The Raman spectra
were recorded on a Bruker FT-Raman spectrometer RFS 100/S using
the 1064 nm line of a Nd:YAG laser. The backscattered (180ꢃ) radi-
ation was sampled and analyzed (Stoke range: 50e4000 cmꢁ1). The
powdered sample was measured in a melting point capillary (512
scans and a resolution of 2 cmꢁ1) using a laser power of ꢂ500 mW.
X-ray diffraction data were collected using a Bruker AXS SMART
APEX diffractometer equipped with a CCD area detector APEXII. For
solution and refinement of the crystal structures the programs
SHELXTL (version 6.10) and SADABS (version 2.03) were used. CCDC
770539 contains the supplementary crystallographic data for [4-
FC6H4(C6F5)IF2][BF4] which can be obtained free of charge on ap-
plication to CCDC,12 Union Road, Cambridge CB2 1EZ, UK, (fax þ44-
(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk). C6F5BF2,15 x-
FC6H4IF4,16 and C6F5IF411 were synthesized by literature procedures.
(P(C6F5)3,17 As(C6F5)3,18 Sb(C6F5)3,18 and Bi(C6F5)319) were synthe-
sized analogue to literature by reactions of C6F5MgBr with the cor-
responding element(III) trichlorides in Et2O.
DSC: Tonset¼96.1 ꢃC (endothermic effect: loss of CH2Cl2),
Tonset¼134.3 ꢃC (exothermic effect).
19F NMR (CH3CN, 24 ꢃC) [3-FC6H4(C6F5)IF2]þ
d
: ꢁ73.6 (t, 4J(F(IF)
,
F
2,6)¼11 Hz, IF2, 2F); ꢁ102.9 (m, 1F, 3-FC6H4); ꢁ126.7 (br,
Dn ¼71 Hz, o-C6F5, 2F); ꢁ138.4 (ttt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼
½
8 Hz, 6J(F4,F(IF))¼2 Hz, p-C6F5, 1F); ꢁ155.1 (m, m-C6F5, 2F); [BF4]ꢁ
d:
ꢁ147.7 (s, BF4, 4F).
0
0
1H NMR (CH3CN, 24 ꢃC) [3-FC6H4(C6F5)IF2]þ d: 8.0 (mo, H2 , H6 ,
0
0
H5 , 3H); 7.7 (m, H4 , 1H): CH2Cl2
d
: 5.4 (s); molar ratio [(3-FC6H4)
(C6F5)IF2]þ/CH2Cl2¼100:42.
0
13C NMR (CH3CN, 24 ꢃC) [3-FC6H4(C6F5)IF2]þ d: 164.4 (dm, 1J(C3 ,
0
0
F3 )¼257 Hz, 3-FC6H4, C3 ), 147.9 (dm, 1J(C4,F4)¼264 Hz, C6F5, C4);
146.8 (dm, 1J(C2,F2)¼1J(C6,F6)¼261 Hz, C6F5, C2,6); 139.4 (dm, 1J(C3,
0
F3)¼1J(C5,F5)¼255 Hz, C6F5, C3,5); 135.8 (m, 3-FC6H4, C1 ); 134.6
0
0
0
0
0
(dm, 1J(C5 ,H5 )¼173 Hz, 3-FC6H4, C5 ); 127.4 (dm, 1J(C6 ,H6 )¼178 Hz,
0
0
0
0
5.2. [2-FC6H4(C6F5)IF2][BF4]
3-FC6H4, C6 ); 124.5 (dm, 1J(C4 ,H4 )¼168 Hz, 3-FC6H4, C4 ); 118.6
0
0
0
(dm, 1J(C2 ,H2 )¼177 Hz, 3-FC6H4, C2 ); 114.0 (m, C6F5, C1).
11B NMR (CH3CN, 24 ꢃC) [BF4]ꢁ d: ꢁ1.3 (s, BF4).
A cold solution (ꢁ78 ꢃC) of C6F5BF2 (1.10 mmol) in CH2Cl2
(1.3 mL) was added in portions to a cold (ꢁ40 ꢃC) vigorously stirred
suspension of 2-FC6H4IF4 (329 mg,1.10 mmol) in CH2Cl2 (3 mL). The
suspension was warmed to 20 ꢃC and after 1.5 h the mother liquor
was separated and the solid residue washed with 1 mL CH2Cl2. The
solid was pumped in vacuum at 20 ꢃC and gave 274 mg of a mixture
of [2-FC6H4(C6F5)IF2][BF4] (0.488 mmol, 44%) and [2-FC6H4(C6F5)I]
[BF4] (0.040 mmol, 4%), which contained still small quantities of
CH2Cl2 (1H NMR).
Raman (20 ꢃC)
n
: 84 (100), 132 (39), 154 (21), 179 (47), 242 (39),
270 (32), 349 (13), 381 (28), 440 (24), 493 (45), 518 (17), 554 (90),
587 (29), 615 (4), 645 (13), 766 (17), 800 (4), 830 (9), 994 (44), 1039
(14), 1071 (6),1102 (5),1167 (8), 1226 (8),1277 (3),1410 (3), 1476 (2),
1518 (3), 1572 (9), 1596 (5), 1636 (12), 3092 (26) cmꢁ1
.
Co-crystallized CH2Cl2 could be removed totally from the solid
by pumping further 5 h at 20 ꢃC, 30 min at 80 ꢃC, and 5 min at 95 ꢃC
in vacuum (3ꢅ10ꢁ2 h Pa). After this treatment no CH2Cl2 could be
detected by 1H NMR. The 19F and 1H NMR spectra of the iodonium
(V) salt was not changed after thermal treatment.
DSC: Tonset¼197.4 ꢃC (exothermic effect).
19F NMR (MeCN, 24 ꢃC) [2-FC6H4(C6F5)IF2][BF4]
d
: ꢁ66.6 (tdd, 4J
0
(F(IF),F2,6)¼14 Hz, 4J(F(IF),F2 )¼14 Hz, 6J(F(IF),F4)¼2 Hz, IF2, 2F); ꢁ98.9
DSC Tonset: 132.7 ꢃC (exothermic effect).

5766
H.-J. Frohn et al. / Tetrahedron 66 (2010) 5762e5767
5.4. [4-FC6H4(C6F5)IF2][BF4]
[BF4]ꢁ
d
: ꢁ145.9 (s, BF4, 4F); molar ratio of the products: [(4-
FC6H4)2IF2]þ/[(4-FC6H4)2I]þ/[BF4]ꢁ¼91:9:104.
A cold (ꢁ30 ꢃC) solution of C6F5BF2 (2.59 mmol) in CH2Cl2
(3.5 mL) was added to a stirred 4-FC6H4IF4 solution (0.75 g,
2.52 mmol) in CH2Cl2 (3 mL, ꢁ30 ꢃC). A suspension resulted when
warmed to 10 ꢃC within 3 h. The solid product was isolated and
washed four times with CH2Cl2 (each 1 mL). Colorless [4-
FC6H4(C6F5)IF2][BF4] was pumped in vacuum at 20 ꢃC for 2 h. Yield
0.75 g, 1.45 mmol, 58%. Single crystals were obtained directly from
the reaction mixture.
1H NMR (CH3CN, 24 ꢃC) [(4-FC6H4)2IF2]þ d: 8.1 (dd, 3J(H2,H3)¼3J
(H6,H5)¼9 Hz, 4J(H2,6,F4)¼4 Hz, H2,6, 4H); 7.6 (dd, 3J(H3,H2)¼3J(H5,
H6)¼9 Hz, 3J(H3,5,F4)¼8 Hz, H3,5, 4H); [(4-FC6H4)2I]þ
d
: 8.1 (dd, 3J
(H2,H3)¼3J(H6,H5)¼9 Hz, 4J(H2,6,F4)¼5 Hz, H2,6, 4H); 7.3 (dd, 3J(H3,
H2)¼3J(H5,H6)¼9 Hz, 3J(H3,5,F4)¼9 Hz, H3,5, 4H); CH2Cl2
d: 5.4
(s, 2H); molar ratio [(4-FC6H4)2IF2]þþ[(4-FC6H4)2I]þ/CH2Cl2¼100:8.
13C NMR (CH3CN, 24 ꢃC) [(4-FC6H4)2IF2]þ d: 167.3 (dm, 1J(C4,F4)¼
258 Hz, C4); 133.4 (m, C1); 133.2 (dm, 1J(C2,H2)¼1J(C6,H6)¼176 Hz,
DSC: Tonset¼142.6 ꢃC (exothermic effect).
C
2,6); 120.9 (ddd, 1J(C3,H3)¼1J(C5,H5)¼172 Hz, 2J(C3,5,F4)¼24 Hz, 2J
19F NMR (CH3CN, 24 ꢃC) [4-FC6H4(C6F5)IF2]þ
d
: ꢁ74.0 (t, 4J(F(IF)
,
(C3,H2)¼2J(C5,H6)¼4 Hz, C3,5).
F
2,6)¼11 Hz, IF2, 2F); ꢁ99.6 (m, 4-FC6H4,1F); ꢁ127.4 (br, Dn ¼84 Hz,
11B NMR (CH3CN, 24 ꢃC) [BF4]ꢁ d: ꢁ1.4 (s, BF4).
½
o-C6F5, 2F); ꢁ138.7 (ttt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼9 Hz, 6J(F4,
F
(IF))¼2 Hz, p-C6F5, 1F); ꢁ155.5 (m, m-C6F5, 2F); [BF4]ꢁ
d: ꢁ146.3 (s,
5.7. Testing of the fluoro-oxidizer potential of [4-FC6H4(C6F5)
IF2][BF4]
4F, BF4).
0
1H NMR (CH3CN, 24 ꢃC) [4-FC6H4(C6F5)IF2]þ
d
: 8.3 (dd, 3J(H2 ,
0
0
0
0
0
0
0
0
H3 )¼3J(H6 ,H5 )¼10 Hz, 4J(H2 ,60,F4)¼4 Hz, H2 ,60, 2H); 7.7 (dd, 3J(H3 ,
5.7.1. Reactions of [4-FC6H4(C6F5)IF2][BF4] with E(C6F5)3 (E¼P, As, Sb,
Bi) in MeCN at 20 ꢃC. The following MeCN solutions of E(C6F5)3
were prepared in FEP-inliners: (a) P(C6F5)3 (89 mg, 0.17 mmol)/
0
0
0
0
0
H2 )¼3J(H5 ,H6 )¼10 Hz, 3J(H3 ,5 ,F4)¼8 Hz, H3 ,5 , 2H).
0
13C NMR (CH3CN, 24 ꢃC) [4-FC6H4(C6F5)IF2]þ d: 167.8 (dtt, 1J(C40 ,
0
0
0
0
0
0
0
F4 )¼259 Hz, 2J(C4 ,H3 ,5 )¼10 Hz, 3J(C4 ,H2 ,6 )¼4 Hz, 4-FC6H4, C4 ),
148.0 (dm, 1J(C4,F4)¼265 Hz, C6F5, C4); 146.9 (dm, 1J(C2,F2)¼1J(C6,
F6)¼260 Hz, C6F5, C2,6); 139.6 (dm, 1J(C3,F3)¼1J(C5,F5)¼258 Hz, C6F5,
600
(96 mg, 0.15 mmol)/500
500 L. Separately the corresponding [4-FC6H4(C6F5)IF2][BF4] so-
lutions were prepared each in 300 L: (a) 40 mg, 0.078 mmol, (b)
mL, (b) As(C6F5)3 (75 mg, 0.13 mmol)/500
mL, (c) Sb(C6F5)3
mL, (d) Bi(C6F5)3 (106 mg, 0.149 mmol)/
m
0
0
0
0
0
0
C
3,5); 134.4 (dm, 1J(C2 ,H2 )¼1J(C6 ,H6 )¼177 Hz, 4-FC6H4, C2 ,6 );
m
0
0
0
0
0
129.1 (m, 4-FC6H4, C1 ); 121.4 (ddd, 1J(C3 ,H3 )¼1J(C5 ,H5 )¼173 Hz, 2J
42 mg, 0.082 mmol, (c) 38 mg, 0.075 mmol, (d) 40 mg, 0.077 mmol.
After mixing of the four combinations the reaction progress was
monitored by 19F NMR till all [4-FC6H4(C6F5)IF2][BF4] was
consumed.
0
0
0
0
0
0
0
0
0
(C3 ,5 ,F4 )¼25 Hz, 2J(C3 ,H2 )¼2J(C5 ,H6 )¼4 Hz, 4-FC6H4, C3 ,5 ); 114.1
(m, C6F5, C1).
11B NMR (CH3CN, 24 ꢃC) [BF4]ꢁ
d
: ꢁ1.5 (s, Dn ¼2 Hz).
½
Raman (20 ꢃC)
n
: 84 (100), 141 (39), 163 (27), 189 (67), 237 (52),
19
255 (16), 269 (17), 314 (7), 335 (10), 355 (18), 374 (23), 441 (25), 495
(50), 542 (83), 565 (39), 588 (28), 621 (18), 763 (14), 807 (16), 821
(11), 986 (15), 997 (14), 1026 (20), 1104 (5), 1163 (17), 1254 (8), 1297
(3), 1407 (5), 1475 (7), 1523 (4), 1577 (11), 1593 (8), 1637 (11), 3090
(a) F NMR (CH3CN, 24 ꢃC, after 9 d)
(C6F5)3PF2
d
: 2.5 (dhep, 1J(F(PF),P)¼690 Hz, 4J(F(PF), F2,6)¼16 Hz,
PF2, 2F); ꢁ132.8 (m, o-C6F5, 6F); ꢁ146.2 (t, 3J(F4,F3,5)¼20 Hz, p-C6F5,
(26), 3118 (10) cmꢁ1
.
3F); ꢁ159.3 (m, m-C6F5, 6F); (C6F5)3P : ꢁ130.2 (m, o-C6F5, 6F);
d
ꢁ149.0 (mo, p-C6F5, 3F);e160.8 (m, m-C6F5, 6F); (C6F5)3PO
d:
ꢁ132.1 (m, o-C6F5, 6F); ꢁ143.4 (m, p-C6F5, 3F); ꢁ159.0 (m, m-C6F5,
5.5. Reaction of C6F5IF4 with 4-FC6H4BF2
6F); [4-FC6H4(C6F5)I]þ
d: ꢁ102.8 (m, 4-FC6H4, 1F); ꢁ121.3 (m, o-
C6F5, 2F); ꢁ142.5 (tt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼6 Hz, p-C6F5, 1F);
When a cold (ꢁ45 ꢃC) solution of 4-FC6H4BF2 (0.13 mmol) in
ꢁ155.9 (m, m-C6F5, 2F); [BF4]ꢁ
d
: ꢁ149.0 (so, BF4, 4F); HF : ꢁ182.2
d
CH2Cl2 (700
CH2Cl2 (200
mL) was mixed with C6F5IF4 (43 mg, 0.12 mmol) in
m
which was warmed to 15 ꢃC within 7 h. After 101 h at 20 ꢃC CH2Cl2
was removed in vacuum and the composition of the black residue
was characterized by 19F NMR in MeCN solution.
(d, 1J(F,H)¼484 Hz); molar ratio of products: (C6F5)3PF2/(C6F5)3P/
L, ꢁ45 ꢃC), immediately a black suspension resulted,
(C6F5)3PO/[4-FC6H4(C6F5)I]þ/HF/[BF4]ꢁ¼20:40:10:30:27:31.
19
(b) F NMR (CH3CN, 24 ꢃC, after 3.5 h)
19F NMR (MeCN, 24 ꢃC) [4-FC6H4(C6F5)IF2]þ see above,
(C6F5)3AsF2
d
: ꢁ22.1 (hep, 4J(F(AsF),F2,6)¼13 Hz, AsF2, 2F); ꢁ131.7
[4-FC6H4(C6F5)I]þ
d: ꢁ102.8 (m, 4-FC6H4, 1F); ꢁ121.1 (m, o-C6F5,
(m, o-C6F5, 6F); ꢁ144.7 (t, 3J(F4,F3,5)¼20 Hz, p-C6F5, 3F);e157.9 (m, m-
2F); ꢁ142.4 (tt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼6 Hz, p-C6F5, 1F);
C6F5, 6F); (C6F5)3As
d
: ꢁ128.1 (m, o-C6F5, 6F); ꢁ149.8 (t, 3J(F4,F3,5)¼
ꢁ155.8 (m, m-C6F5, 2F); C6F5I
d
: ꢁ120.1 (m, o-C6F5, 2F); ꢁ153.3 (tt, 3J
20 Hz, p-C6F5, 3F); ꢁ160.3 (m, m-C6F5, 6F); [4-FC6H4(C6F5)I]þ
d:
(F4,F3,5)¼19 Hz, 4J(F4,F2,6)¼2 Hz, p-C6F5,1F); ꢁ160.1 (m, m-C6F5, 2F);
ꢁ102.6 (m, 4-FC6H4,1F); ꢁ121.0 (m, o-C6F5, 2F);e142.3 (tt, 3J(F4,F3,5)¼
[BF4]ꢁ
d
: ꢁ147.3 (s, BF4, 4F); molar ratio [4-FC6H4(C6F5)IF2]þ/
20 Hz, 4J(F4,F2,6)¼6 Hz, p-C6F5, 1F); ꢁ155.6 (m, m-C6F5, 2F); [BF4]ꢁ
d:
[4-FC6H4(C6F5)I]þ/C6F5I/[BF4]ꢁ¼52:46:3:97.
ꢁ148.5 (s, Dd
(
10BF4e11BF4)¼0.053, BF4, 4F); molar ratio of products:
(C6F5)3AsF2/(C6F5)3As/[4-FC6H4(C6F5)I]þ/[BF4]ꢁ¼37:24:39:39.
5.6. [(4-FC6H4)2IF2][BF4]
19
(c) F NMR (CH3CN, 24 ꢃC, after 0.5 h)
A cold (ꢁ78 ꢃC) solution of 4-FC6H4BF2 (1.4 mmol) in CH2Cl2
(3 mL) was added in three portions to a cold (e45 ꢃC) suspension of
4-FC6H4IF4 (410 mg, 1.38 mmol) in CH2Cl2 (3.5 mL). Spontaneously
a black suspension was formed, which was warmed to 20 ꢃC. After
170 min the black solid was separated from the mother liquor,
(C6F5)3SbF2
d
: ꢁ79.1 (br, Dn ¼95 Hz, SbF2, 2F); ꢁ126.1 (br,
½
Dn ¼45 Hz, o-C6F5, 6F); ꢁ144.2 (br, Dn ¼111 Hz, p-C6F5, 3F);
½
½
ꢁ157.1 (br, Dn ¼59 Hz, m-C6F5, 6F); (C6F5)3Sb : ꢁ121.8 (m, o-C6F5,
d
½
6F); ꢁ150.5 (tt, 3J(F4,F3,5)¼19 Hz, 4J(F4,F2,6)¼3 Hz, p-C6F5, 3F);
washed with CH2Cl2 (100
m
L), and pumped in vacuum at 20 ꢃC for
ꢁ160.4 (m, m-C6F5, 6F); [4-FC6H4(C6F5)I]þ
: ꢁ102.8 (m, 4-FC6H4,
d
60 min. The solid (270 mg) contained [(4-FC6H4)2IF2][BF4] (244 mg,
0.54 mmol, 39%), [(4-FC6H4)2I][BF4] (26 mg, 0.06 mmol, 5%), and
still small quantities of CH2Cl2.
1F); ꢁ120.3 (m, o-C6F5, 2F); ꢁ142.5 (tt, 3J(F4,F3,5)¼20 Hz, 4J(F4,F2,6)¼
6 Hz, p-C6F5, 1F); ꢁ155.9 (m, m-C6F5, 2F); [BF4]ꢁ
: ꢁ149.0 (s, BF4,
d
4F); molar ratio of products: (C6F5)3SbF2/(C6F5)3Sb/[4-FC6H4(C6F5)
DSC: Tonset¼187.9 ꢃC (exothermic effect).
I]þ/[BF4]ꢁ¼22:53:25:23.
19F NMR (CH3CN, 24 ꢃC) [(4-FC6H4)2IF2]þ
d
: ꢁ85.3 (m, IF2, 2F);
ꢁ100.5 (m, 4-FC6H4, 2F); [(4-FC6H4)2I]þ
d
: ꢁ104.4 (m, 4-FC6H4, 2F);
(d) F NMR (CH3CN, 24 ꢃC, after 70 h)
19

H.-J. Frohn et al. / Tetrahedron 66 (2010) 5762e5767
5767
(C6F5)3Bi
d
: ꢁ117.1 (m, o-C6F5, 6F); ꢁ152.1 (t, 3J(F4,F3,5)¼19 Hz,
ꢁ114.5 (tt, 3J(F4,H3,5)¼9 Hz, 4J(F4,H2,6)¼5 Hz, 4-FC6H4, 1F); 4-
p-C6F5, 3F); ꢁ160.0 (m, m-C6F5, 6F); [4-FC6H4(C6F5)I]þ
d
: ꢁ102.8
FC6H4IOF2
d
: ꢁ27.0 (s, IOF2, 2F); ꢁ103.7 (m, 4-FC6H4, 1F); [BF4]ꢁ
d:
(m, 4-FC6H4, 1F); ꢁ121.3 (m, o-C6F5, 2F);e142.5 (tt, 3J(F4,F3,5)¼
20 Hz, 4J(F4,F2,6)¼6 Hz, p-C6F5, 1F); ꢁ155.9 (m, m-C6F5, 2F);
ꢁ148.4 (s, BF4, 4F); molar ratio of products: 4-FC6H4IF2/[4-
FC6H4(C6F5)I]þ/4-FC6H4I/4-FC6H4IOF2/[BF4]ꢁ¼21:29:48:2:29.
[(C6F5)2I]þ
d
: ꢁ120.4 (m, o-C6F5, 4F); ꢁ141.3 (tt, 3J(F4,F3,5)¼20 Hz, 4J
(F4,F2,6)¼6 Hz, p-C6F5, 2F); ꢁ155.5 (m, m-C6F5, 4F); C6F5H
d:
Supplementary data
ꢁ139.2 (m, o-C6F5, 2F); ꢁ154.8 (t, 3J(F4,F3,5)¼19 Hz, p-C6F5, 1F);
ꢁ162.7 (m, m-C6F5, 2F); 1,4-F2C6H4 d: ꢁ119.6 (tt, 3J(F,H)¼6 Hz, 4J(F,
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2010.04.047.
H)¼6 Hz, 2F); [BF4]ꢁ
d: ꢁ148.8 (s, Dd
(
10BF4e11BF4)¼0.054, BF4, 4F);
molar ratio of products: (C6F5)3Bi/[4-FC6H4(C6F5)I]þ/[(C6F5)2I]þ/
C6F5H/1,4-F2C6H4 /[BF4]ꢁ¼46:7:22:24:13:31.
References and notes
5.7.2. Reactions of [4-FC6H4(C6F5)IF2][BF4] with ArI (Ar¼C6F5I, (a) or
1. (a) Beringer, F. M.; Gindler, E. M. Organic Compounds of Polyvalent Iodine.
Iodine Abstr. Rev.; Chilean Iodine Educational Bureau: New York, NY, 1956;
Vol. 3, 1e70; (b) Varvoglis, A. The Organic Chemistry of Polycoordinated Iodine;
VCH: Weinheim, 1992; pp 207e306.
2. Masson, I.; Race, E.; Pounder, F. E. J. Chem. Soc. 1935, 1669e1670.
3. Beringer, F. M.; Bodlaender, P. J. Org. Chem. 1968, 33, 2981e2984.
4. Lyalin, V. V.; Orda, V. V.; Alekseeva, L. A.; Yagupol’skii, L. M. Zh. Org. Khim. 1972,
8, 210e211.
4-FC6H4 (b)) in MeCN at 20 ꢃC. 16
mL, 0.12 mmol C6F5I (a) or 14 mL,
0.12 mmol 4-FC6H4I (b) was added to solutions of [4-FC6H4(C6F5)
IF2][BF4] in MeCN: (a) 31 mg, 0.060 mmol in 300 L (a) or 26 mg,
m
0.051 mmol in 300 mL (b). After mixing of the two combinations the
reaction progress was monitored by 19F NMR till all [4-FC6H4(C6F5)
IF2][BF4] was consumed.
5. Hoyer, S. Dissertation, FU Berlin, 2004.
6. Helber, J.; Frohn, H.-J.; Klose, A.; Scholten, T. Arkivoc Online Vers.: http://www.
arkat-usa.org/ark/journal/2003/Varvoglis/AV-682A/682.htm; Arkivoc Print Vers.
(ISSN 1424-6369) 2003, Part VI, 71e82.
19
(a) F NMR (CH3CN, 24 ꢃC, after 11 d)
€
7. Frohn, H.-J.; Wenda, A.; Florke, U. Z. Anorg. Allg. Chem. 2008, 634, 764e770.
C6F5IF2 d: ꢁ122.1 (m, o-C6F5, 2F); ꢁ143.7 (m, p-C6F5, 1F); ꢁ156.2
8. Frohn, H.-J.; Bardin, V. V. In Recent Developments in Carbocation and Onium Ion
Chemistry; Laali, K. K., Ed.; ACS Symposium Series 965; ACS: Washington, DC,
2007; pp 428e457.
9. Frohn, H.-J.; Hirschberg, M.; Wenda, A.; Bardin, V. V. J. Fluorine Chem. 2008, 129,
459e473.
(m, m-C6F5, 2F); ꢁ159.4 (so, IF2, 2F); [4-FC6H4(C6F5)I]þ
: ꢁ102.0
d
(mo, 4-FC6H4, 1F); ꢁ120.4 (m, o-C6F5, 2F); ꢁ141.7 (m, p-C6F5, 1F);
ꢁ155.1 (m, m-C6F5, 2F); [4-FC6H4(C6F5)IO]þ
: ꢁ102.1 (mo, 4-FC6H4,
d
1F); ꢁ128.1 (m, o-C6F5, 2F); ꢁ140.5 (m, p-C6F5, 1F); ꢁ155.7 (m, m-
10. Frohn, H.-J.; Bailly, F.; Bardin, V. V. Mendeleev Commun. 2009, 19, 67e68.
C6F5, 2F); C6F5I
d
: ꢁ119.3 (m, o-C6F5, 2F); ꢁ152.6 (t, 3J(F4,F3,5)¼20 Hz,
€
€
11. Frohn, H.-J.; Gorg, S.; Henkel, G.; Lage, L. Z. Anorg. Allg. Chem. 1995, 621,
p-C6F5, 1F); ꢁ159.4 (mo, m-C6F5, 2F); [BF4]ꢁ
: ꢁ147.3 (s, BF4, 4F);
d
1251e1256.
12. Abo-Amer, A.; Frohn, H.-J.; Steinberg, C.; Westphal, U. J. Fluorine Chem. 2006,
127, 1311e1323.
13. Bondi, A. J. Phys. Chem. 1964, 68, 441e451.
14. Bailly, F.; Barthen, P.; Breuer, W.; Frohn, H.-J.; Giesen, M.; Helber, J.; Henkel, G.;
Priwitzer, A. Z. Anorg. Allg. Chem. 2000, 626, 1406e1413.
15. Frohn, H.-J.; Franke, H.; Fritzen, P.; Bardin, V. V. J. Organomet. Chem. 2000, 598,
127e135.
molar ratio of products: C6F5IF2/[4-FC6H4(C6F5)I]þ/[4-FC6H4(C6F5)
IO]þ/C6F5I/[BF4]ꢁ¼13:22:12:53:34.
19
(b) F NMR (CH3CN, 24 ꢃC, after 71 h)
16. Frohn, H. -J.; Abo-Amer, A. A. DE Patent 10232323A1, 2004.
17. Wall, L. A.; Donadio, R. E.; Pummer, W. J. J. Am. Chem. Soc. 1960, 82, 4846e4848.
18. Fild, M.; Glemser, O.; Christoph, G. Angew. Chem. 1964, 76, 953.
19. Royo, P.; Uson, R. Rev. Acad. Cienc. Exactas, Fis-Quim. Natur. Zaragoza 1969, 24,
119e122.
4-FC6H4IF2
d
: ꢁ107.8 (m, 4-FC6H4, 1F); ꢁ171.2 (s, IF2, 2F); [4-
FC6H4(C6F5)I]þ
d
: ꢁ102.7 (tt, 3J(F4,H3,5)¼9 Hz, 4J(F4,H2,6)¼4 Hz, 4-
FC6H4, 1F); ꢁ121.2 (m, o-C6F5, 2F); ꢁ142.4 (tt, 3J(F4,F3,5)¼20 Hz, 4J
(F4,F2,6)¼6 Hz, p-C6F5, 1F); ꢁ155.7 (m, m-C6F5, 2F); 4-FC6H4I
d: