Synthesis and characterization of 2,6-difluorophenyliodine(III) derivatives

Article abstract of DOI:10.1016/S0022-1139(99)00118-9

2,6-F₂C₆H₃IF₂ was isolated in quantitative yield from the reactions of 2,6-F₂C₆H₃I and XeF₂ or F₂/N₂-mixtures. Ligand exchange using (CF₃

Full text of DOI:10.1016/S0022-1139(99)00118-9

Journal of Fluorine Chemistry 99 (1999) 9±15
Synthesis and characterization of 2,6-di¯uorophenyliodine(III)
derivatives
Vasilios Padelidakis, Wieland Tyrra, Dieter Naumann*
È È È È
Institut fur Anorganische Chemie, Universitat zu Koln, Greinstr. 6, D-50939 Koln, Germany
Received 29 March 1999; accepted 7 May 1999
Dedicated to Prof. Friedo Huber on the occasion of his 70th birthday
Abstract
2,6-F2C6H3IF2 was isolated in quantitative yield from the reactions of 2,6-F2C6H3I and XeF2 or F2/N2-mixtures. Ligand exchange using
(CF3CO)2O gave the corresponding bis(tri¯uoroacetate) in 84% yield. The reaction of 2,6-F2C6H3I(OCOCF3)2 and 1,3-F2C6H4 in the
presence of CF3SO3H selectively gave [I(2,6-F2C6H3)2][OSO2CF3] in 80% yield.
Ligand exchange reactions of 2,6-F2C6H3IF2 and triarylboranes in the presence of stoichiometric amounts of BF3ÁO(CH3)2 gave the
corresponding 2,6-di¯uorophenyl(aryl)iodine(III) tetra¯uoroborates in 45±85% yield.
Ligand exchange of the tetra¯uoroborate was studied for some examples using (CH3)3SiOSO2CF3 or (CH3)3SiOCOCF3 giving the
corresponding 2,6-di¯uorophenyl(aryl)iodine(III) tri¯uoromethanesulfonates or tri¯uoroacetates in nearly quantitative yields.
All compounds were characterized by their NMR and mass spectra and melting and decomposition points. # 1999 Elsevier Science S.A.
All rights reserved.
Keywords: Fluorine; Iodine; 2,6-Di¯uorophenyliodine(III) compounds
1. Introduction
2. Results and discussion
Aryliodine(III) derivatives have been known for more
than a century [1] and have been the subject of several
reviews [2,3] and monographs [4±6]. Fully ¯uorinated and
partially ¯uorinated aryliodine(III) compounds have been
synthesized by different routes, e.g.:
2.1. Oxidation reactions of 2,6-F2C6H3I
2,6-F2C6H3IF2 was easily prepared from 2,6-F2C6H3I
either by direct ¯uorination or reaction with XeF2. These
oxidative ¯uorinations are comparable to the well-known
syntheses of C6F5IF2 [7,8].
ArfIF2: oxidative fluorination of fluoroiodobenzenes [7±
10]; ligand exchange reactions of IF3 and Cd(C6F5)2
[11]; fluorination of C6F5IO using SF4 [12].
0
‡
[IArf(Arf )]X: oxidative arylation of iodobenzenes using
[XeArf] [13±15]; ligand exchange reactions on arylio-
dine difluorides [15] and iodine trifluoride [11] using
triarylboranes; reaction of C6F5SiF3 with [IF4][SbF6] in
FSO3H [16]; electrophilic substitutions starting with
I(OCOCF3)3 and a fluorobenzene in the presence of a
strong acid, e.g. CF3SO3H [17].
2,6-F2C6H3IF2 was obtained in quantitative yield as a
white solid melting at 1648C without decomposition and
was chosen as starting material for the synthesis of a series
of mono- and diaryliodine(III) derivatives.
Herein we report on the syntheses of a number of new
aryliodine(III) compounds with the 2,6-F2C6H3-ligand
(Scheme 1).
2.2. Fluorine-trifluoroacetate exchange with (CF3CO)2O
2,6-F2C6H3IF2 was converted into 2,6-F2C6H3I(O-
COCF3)2 with (CF3CO)2O via the well-established method
*Corresponding author. Fax: +49-0221-470-5196.
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 1 1 8 - 9

10
V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
Scheme 1. Survey of reactions.
for per¯uoroorganoiodine(III) compounds [18]:
sulfonic acid gave bis(2,6-di¯uorophenyl)iodine tri¯uoro-
methanesulfonate,[I(2,6-F2C6H3)2][OSO2CF3],in80%yield.
The process must be regarded as electrophilic aromatic
substitution.
This synthetic approach has to be considered as a com-
bination of two well known reactions described by Ume-
moto et al. [19] and our group [17]. This method had already
been successfully applied to the synthesis of arylxenon(II)
derivatives starting from Xe(OCOCF3)2 and ¯uorine, tri-
¯uoromethyl or nitro substituted benzenes in the presence of
CF3SO3H or FSO3H [20,21].
2; 6-F2C6H3IF2 ‡ 2ꢀCF3CO†2O
! 2; 6-F2C6H3IꢀOCOCF3† ‡ 2CF3COF
2
2,6-F2C6H3I(OCOCF3)2 was easily separated from vola-
tile CF3COF and excess (CF3CO)2O and isolated in 85%
yield as a white solid melting at 1518C.
2.3. Synthesis of diaryliodine trifluoromethanesulfonates
via electrophilic aromatic substitution
The reaction of 2,6-F2C6H3I(OCOCF3)2 and 1,3-F2C6H4
in the presence of CF3SO3H proceeded in CF3COOH, and
[I(2,6-F2C6H3)2][OSO2CF3] was isolated after a reaction
The reaction of 2,6-di¯uorophenyliodine bis(tri¯uoroa-
cetate) and 1,3-F2C6H4 in the presence of tri¯uoromethane-

V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
11
time of 2 days as a pale yellow solid. Exact stoichiometry is
necessary to avoid an incomplete reaction or the formation
of unidenti®ed by-products as observed using an excess of
tri¯uoromethanesulfonic acid.
In extension of our previous work, tri¯uoromethanesul-
fonates and tri¯uoroacetates were prepared via exchange
of the tetra¯uoroborate anion using (CH3)3SiOSO2CF3
and (CH3)3SiOCOCF3, respectively, with formation of
the thermodynamically stable products (CH3)3SiF and
BF3.
2; 6-F2C6H3IꢀOCOCF3† ‡ 1; 3-F2C6H4 ‡ CF3SO3H
2
! ‰Iꢀ2; 6-F2C6H3† ŠOSO2CF3 ‡ 2CF3COOH
These reactions were exemplarily studied for some of the
derivatives.
2
In contrast, the reaction of Xe(OCOCF3)2 and 1,3-
F2C6H4 under similar conditions gave [Xe(2,4-F2C6H3)][O-
SO2CF3] as the major product [20,21]; however, no spectro-
scopic evidence was found for [I(2,6-F2C6H3)(2,4-
F2C6H3)][OSO2CF3] in reactions starting with 2,6-
F2C6H3I(OCOCF3)2. An explanation for this different reac-
tion behaviour cannot be given.
‰Iꢀ2; 6-F2C6H3†Ar0fŠ‰BF4Š ‡ ꢀCH3†3SiOSO2CF3
! ‰Iꢀ2; 6-F2C6H3†Ar0fŠ‰OSO2CF3Š ‡ ꢀCH3†3SiF ‡ BF3
Ar0f ˆ 2; 4; 6-F3C6H2; 4-FC6H4
‰Iꢀ2; 6-F2C6H3†Ar0f0Š‰BF4Š ‡ ꢀCH3†3SiOCOCF3
! ‰Iꢀ2; 6-F2C6H3†Ar0f0Š‰OCOCF3Š ‡ ꢀCH3†3SiF ‡ BF3
Ar0f0 ˆ 2; 6-F2C6H3; 2; 4; 6-F3C6H2
2.4. Synthesis of diaryliodine(III) tetrafluoroborates
starting from aryliodine difluorides and
triarylboranes
The exchange was complete in acetonitrile solution
within 2±6 days. The products were isolated as stable pale
yellow to white solids after distilling off all volatile com-
ponents in vacuo.
Diaryliodine(III) tetra¯uoroborates are accessible from
reactions of aryliodine(III) di¯uorides and triarylboranes in
the presence of stoichiometric amounts of BF3ÁO(CH3)2.
This method was earlier applied for the synthesis of
[I(C6F5)2][BF4] and the non-symmetrical species
[I(C6F5)(2,4,6-F3C6H2)][BF4] [14] by analogy to the reac-
tions of XeF2 and triarylboranes in the presence of
BF3ÁO(CH3)2 to yield arylxenon(II) tetra¯uoroborates
[13,22±25].
2.6. Comparison of some properties of the new
aryliodine(III) compounds
2.6.1. Thermal stability
All 2,6-di¯uorophenyliodine(III) compounds synthesized
are stable solids. The melting and decomposition points are
above 1508C and exhibit some interesting gradations
depending on the groups attached to the 2,6-F2C6H3I unit.
In the series of different [I(2,6-F2C6H3)2] salts thermal
stability increases from the tetra¯uoroborate (dec. p. 2298C)
via the tri¯uoroacetate (dec. p. 2888C) to the tri¯uorometha-
nesulfonate (dec. p. > 3508C).
Within the group of mixed diaryliodine(III) tetra¯uoro-
borates, [I(2,6-F2C6H3)(C6F5)][BF4] is the most stable. The
decomposition point of 3228C is about 1008C higher
than the decomposition points of the other derivatives
(Table 4).
Now we synthesized several compounds of the general
formula [I(2,6-F2C6H3)Arf][BF4] (Arf=C6F5, 2,4,6-F3C6H2,
2,6-F2C6H3, 2-FC6H4, 3-FC6H4, 4-FC6H4) according to
3ꢀ2; 6-F2C6H3†IF2 ‡ BꢀArf† ‡ 2BF3
3
! 3‰Iꢀ2; 6-F2C6H3†ArfŠ‰BF4Š
These reactions were performed in CH2Cl2 to precipitate
the insoluble products. The addition of BF3ÁO(CH3)2 to the
reaction mixtures supports the exclusive formation of salts
with the tetra¯uoroborate anion and avoids the formation of
mixed aryl¯uoroborates. On the other hand the Lewis-acid
BF3 accelerates the reaction probably forming an adduct
with 2,6-F2C6H3IF2 with simultaneous weakening of one I±
F bond.
The remarkable stability of the diaryliodine(III) tetra-
¯uoroborates is demonstrated by their decomposition points
distinctly above 2008C. The high stability might be
explained by delocalization of the positive charge on the
aromatic ring systems [22].
2.6.2. Mass spectra
Some of the effects in thermal stability are consistent with
effects observed in the mass spectrometric decay. Compar-
ison of the mass spectra of 2,6-F2C6H3I(OCOCF3)2, [I(2,6-
F2C6H3)2][OCOCF3] and [I(2,6-F2C6H3)2][OSO2CF3]
exhibits in the case of the monoaryl compound the peak
‡
[I(C6H3F2)(OCOCF3)] (m/eˆ353) as that of the highest
mass.
The spectra of all [I(2,6-F2C6H3)2] derivatives show the
‡
2.5. Ligand exchange of the tetrafluoroborate anion using
trimethylsilylesters of strong acids
peak of the cation [I(C6H3F2)2] (m/e ˆ 353) and its frag-
ments. In the cases of [I(2,6-F2C6H3)2][OCOCF3] and
[I(2,6-F2C6H3)2][BF4] also fragment peaks of polymer
‡
‡
[I(2,6-F2C6H3)2][OSO2CF3] was also synthesized in an
exchange reaction of the corresponding tetra¯uoroborate,
[I(2,6-F2C6H3)2][BF4], with (CH3)3SiOSO2CF3 in CH3CN
[26].
units such as [C24H9F8I] (m/e ˆ 576) and [C18H7F6I]
(m/e ˆ 464) were detected.
Whereas the tri¯uoromethanesulfonates show an easily
explainable fragmentation [26], the decay of all but one

12
V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
Table 1
NMR chemical shifts and J(19
3. Experimental
F
13 C) of 2,6-F2C6H3I, 2,6-F2C6H3IF2 and
a
2,6-F2C6H3I(OCOCF3)2
All reactions were carried out in carefully dried reaction
vessels using Schlenk-techniques. 2,6-F2C6H3I, 1,3-F2C6H4
and CF3SO3H (freshly distilled) were purchased from
ABCR, (CH3)3SiOCOCF3 and (CH3)3SiOSO2CF3 from
Aldrich, BF3ÁO(CH3)2 from Merck-Schuchardt and used
as received. Elemental ¯uorine, CF3COOH and (CF3CO)2O
were received from Solvay Fluor und Derivate as gifts.
B(Arf)3 and XeF2 were prepared according to literature
procedures [27] and [28], respectively. All solvents were
puri®ed by standard methods [29].
NMR spectra were recorded on Bruker FT-NMR spectro-
meters AC 200 and AMX 300 operating at 200.1 MHz
(300.1 MHz) [1H], 188,3 MHz (282.4 MHz) [19F] and
50.3 MHz (75.5 MHz) [13C]. CCl3F [19F] and (CH3)4Si
[1H, 13C] were used as external standards.
2,6-F2C6H3I
2,6-F2C6H3IF2
2,6-F2C6H3I
(OCOCF3)2
19F: ꢀ(F-2,6)
ꢀ(IF2)
92.1
±
95.9
164.6
±
94.3
±
ꢀ(OCOCF3)
1H: ꢀ(H-3,5)
ꢀ(H-4)
±
73.6
6.85
7.28
71.3
24
7.37
7.79
107.9
25
7.34
7.79
13C: ꢀ(C-1)
2Jꢀ19F 13 C†
ꢀ(C-2,6)
102.6
Broad
160.9
256
163.0
246
6
160.0
255
n.r.
1Jꢀ19F 13 C†
3Jꢀ19F 13 C†
d(C-3,5)
n.r.
114.2
n.r.b
111.9
25a
131.6
10
113.3
23
2Jꢀ19F 13 C†
ꢀ(C-4)
138.6
10
139.7
10
161.1c
113.8d
3Jꢀ19F 13 C†
ꢀ(C=O)
ꢀ(CF3)
±
±
Mass spectra were run on a modi®ed Varian MAT CH5
spectrometer, DTA measurements on a Mettler TA1 ther-
moanalyzer.
±
±
ꢀ in ppm, J in Hz. Solvents CD3CN (1H, 13C) and CH3CN (19F), external
lock (CD3)2CO). n.r. ˆ not resolved.
4Jꢀ19F 13 C† ˆ 3 Hz.
a
3.1. Synthesis of 2,6-F2C6H3IF2
b Signals overlap.
c
2Jꢀ19F 13 C† ˆ 40.2 Hz.
1Jꢀ19F 13 C† ˆ 287.0 Hz.
d
3.1.1. Fluorination of 2,6-F2C6H3I with XeF2
1.0 g (4.1 mmol) 2,6-F2C6H3I were dissolved in 5 ml
CH3CN. A solution of 0.7 g (4.1 mmol) XeF2 in 5 ml
CH3CN was added dropwise. After stirring the reaction
mixture for 24 h at room temperature, the solvent was
distilled off in vacuo. 2,6-F2C6H3IF2 was obtained as a
white solid in quantitative yield.
derivatives of the general formula [I(2,6-F2C6H3)Arf][BF4]
was similar. They decompose under mass spectrometric
conditions with formation of fragments in intensities mainly
less than 10% which could be interpreted as polyphenylio-
dine ions.
Only [I(2,6-F2C6H3)(C6F5)][BF4] showed a fragmenta-
tion pattern comparable with the tri¯uoromethanesulfo-
nates. Besides the cation peak (m/e ˆ 407) the fragments
3.1.2. Fluorination of 2,6-F2C6H3I with F2
4.0 g (16.4 mmol) 2,6-F2C6H3I were suspended in 60 ml
CCl3F. A precooled ¯uorine-gas¯ow diluted with nitrogen
(1 : 10) was bubbled through the solution. After a few
minutes a white solid began to precipitate. The reaction
was stopped as soon as elemental ¯uorine passed through
the reaction vessel without further reaction. After distilling
off the solvent in vacuo at room temperature 2,6-F2C6H3IF2
was obtained as a white solid in quantitative yield.
m.p. 1648C, dec. 1858C. MS (EI, 20 eV, 1008C; m/e): 278
‡
‡
‡
‡
[C6F5I] , [C6H3F2I] , [C6HF5] , [C6H3F3]
and
‡
[C6H3F2] were detected. The ion of highest mass was
‡
[I(C6H3F2)(C6F5)F] (m/e ˆ 426).
2.6.3. NMR spectra
A comparison of the NMR chemical shifts of 2,6-
F2C6H3I, 2,6-F2C6H3IF2 and 2,6-F2C6H3I(OCOCF3)2
(Table 1) exhibits characteristic alteration with the change
of the iodine oxidation state from I to III. At comparable
conditions, the F-2,6-resonance is shifted approximately
2±4 ppm to higher ®eld; high-®eld shifts of ca. 0.5 ppm
are found for all proton resonances. Signi®cant low-®eld
shifts are measured for the C-1-atom (up to 36.6 ppm) and
the C-4-atom (up to 8.1 ppm); the shifts of the C-2,6- and
C-3,5-atoms remain nearly unaffected by the change of
oxidation states.
‡
‡
‡
(5%, [F2C6H3IF2] ˆM ), 259 (8%, [F2C6H3IF] ), 240
‡
‡
(100%, [F2C6H3I] ), 132 (62%, [F3C6H3] ), 113 (44%,
[F2C6H3] ).
NMR data are summarized in Table 1.
‡
3.2. Synthesis of 2,6-F2C6H3I(OCOCF3)2
1.4 g (5.0 mmol) 2,6-F2C6H3IF2 was suspended in 10 ml
(CF3CO)2O. After stirring the reaction mixture for 48 h at
room temperature, all volatile components, mainly
(CF3CO)2O and CF3COF, were distilled off in vacuo.
2,6-F2C6H3I(OCOCF3)2 was obtained as a white solid in
85% (1.98 g) yield.
m.p. 1518C, Sublimation: 1108C at 10 3 bar. MS (EI,
17 eV, 908C; m/e): 353 (71%, [I(F2C6H3)(OCOCF3)] ), 240
The NMR chemical shifts of the 2,6-F2C6H3-group of the
diaryl derivatives are neither in¯uenced by different anions
nor different ¯uorophenyl groups attached to the iodine
center (Tables 3 and 4). However, the C-1 chemical shifts of
‡
[I(2,6-F2C6H3)Arf] and 2,6-F2C6H3IX2 (X ˆ F, OCOCF3)
‡
differ by ca. 17 and 12 ppm, respectively.

V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
13
‡
‡
(100%, [F2C6H3I] ), 226 (53%, [F2C6H3OCOCF3] or
‡
3.4.1. Mass spectra
[I(2,6-F2C6H3)2][BF4] (EI, 15 eV, 1908C; m/e): 686 (7%,
[C30H9F10I] ), 574 (8%, [C24H7F8I] ), 463 (8%,
‡
‡
[(F2C6H3)2] ), 113 (39%, [F2C6H3] or [CF3CO2] ).
NMR data are summarized in Table 1.
Elemental analysis for C10H3F8IO4 [found (calculated)] I:
26.7 (27.3)%; F: 33.4 (32.6)%.
‡
‡
‡ ‡
[C18H6F6I] ), 351 (12%, [C12H4F4I] ), 239 (100%,
‡
‡
‡
[C6H2F2I] ), 127 (2%, [I] ), 113 (24%, [C6H3F2] ).
[I(2,6-F2C6H3)(C6F5)][BF4] (EI, 17 eV, 608C; m/e): 426
(15%, [I(C6H3F2)(C6F5)F] ), 407 (31%, [I(C6H3F2)-
‡
3.3. Synthesis of [I(2,6-F2C6H3)2][OSO2CF3]
‡
‡
‡
(C6F5)] ), 294 (74%, [C6F5I] ), 240 (98%, [C6H3F2I] ),
‡
‡
1.1 g (2.4 mmol) 2,6-F2C6H3I(OCOCF3)2 was suspended
in 20 ml CF3COOH at 08C and 0.22 ml (2.4 mmol) 1,3-
F2C6H4 were added. After stirring for 1 h and adding
0.21 ml (2.4 mmol) CF3SO3H, the reaction mixture was
allowed to warm up to room temperature and stirred for
an additional 48 h. All volatile compounds were distilled off
in vacuo. [I(2,6-F2C6H3)2][OSO2CF3] remained as a pale
yellow solid in 80% (0.96 g) yield.
168 (20%, [C6HF5] ), 132 (100%, [C6H3F3] ), 113 (11%,
‡
[C6H3F2] ).
[I(2,6-F2C6H3)(2,4,6-F3C6H2)][BF4] (EI, 17 eV, 1808C;
m/e): 500 (4%, [C18H5F8I] ), 482 (5%, [C18H6F7I] ), 370
‡
‡
‡
‡
(9%, [C12H4F5I] ), 352 (3%, [C12H5F4I] ), 258 (86%,
‡
‡
[C6H2F3I] ), 240 (100%, [C6H3F2I] ).
[I(2,6-F2C6H3)(2-FC6H4)][BF4] (EI, 15 eV, 1758C; m/e):
352 (3%, [C12H5F4I] ), 334 (5%, [C12H6F3I] ), 240 (100%,
‡
‡
‡
‡
‡
The analytical data corresponded with those given in
[26].
[C6H3F2I] ), 222 (44%, [C6HFI] ), 114 (11% [C6H4F2] ),
‡
96 (3%, [C6H5F] ).
[I(2,6-F2C6H3)(3-FC6H4)][BF4] (EI, 15 eV, 1508C; m/e):
352 (2%, [C12H5F4I] ), 334 (5%, [C12H6F3I] ), 240 (100%,
‡ ‡
3.4. Synthesis of [I(2,6-F2C6H3)(Arf)][BF4] (Arf ˆ C6F5,
2,4,6-F3C6H2, 2,6-F2C6H3, 2-FC6H4, 3-FC6H4,
4-FC6H4)
‡
‡
‡
[C6H3F2I] ), 222 (28%, [C6H4FI] ), 113 (13%,
‡
[C6H3F2] ), 95 (12%, [C6H4F] ).
[I(2,6-F2C6H3)(4-FC6H4)][BF4] (EI, 15 eV, 1608C; m/e):
446 (3%, [C18H8F5I] ), 352 (5%, [C12H5F4I] ), 334 (5%,
‡ ‡
General procedure: 0.83 g (3.0 mmol) 2,6-F2C6H3IF2
were dissolved in 10 ml CH2Cl2 at 408C. A precooled
mixture ( 408C) of the corresponding borane (ca.
1.0 mmol) and 0.19 ml (2.07 mmol) BF3ÁO(CH3)2 in
20 ml CH2Cl2 were added dropwise. After 1 h the solution
had taken on a brown colour from which a white solid began
to precipitate. For completion of the reaction, the mixture
was stirred for additional 24 h. The solid was ®ltered off at
408C and washed with cold CH2Cl2. After drying the
residue in vacuo, the diaryliodine tetra¯uoroborates were
obtained as white solids.
‡
‡
[C12H6F3I] ), 240 (100%, [C6H3F2I] ), 222 (87%,
‡
‡
‡
[C6H4FI] ), 114 (25%, [C6H4F2] ), 95 (24%, [C6H4F] ).
3.5. Synthesis of [I(2,6-F2C6H3)(2,4,6-
F3C6H2)][OSO2CF3] and [I(2,6-F2C6H3)(2-
FC6H4)][OSO2CF3]
General procedure: The corresponding diaryliodine te-
tra¯uoroborate ([I(2,6-F2C6H3)(2,4,6-F3C6H2)][BF4] 0.77 g
(1.7 mmol);
[I(2,6-F2C6H3)(4-FC6H4)][BF4]
0.14 g
NMR data are summarized in Tables 2 and 3, experi-
mental details, melting and decomposition points in
Table 4.
(0.3 mmol)) was dissolved in 10 ml CH3CN and stoichio-
metric amounts of (CH3)3SiOSO2CF3 dissolved in 10 ml
CH3CN were added dropwise to the solution at 408C.
Table 2
19F-NMR chemical shifts of 2,6-difluorophenyl(fluorophenyl)iodine(III) tetrafluoroboratesa
ꢀ(F-2,6)
ꢀ(F-20)
ꢀ(F-30)
ꢀ(F-40)
ꢀ(F-50)
ꢀ(F-60)
ꢀ([BF4] )
‡
[I(2,6-F2C6H3)(C6F5)]
94.5
94.6
94.9
95.3
94.9
95.3
121.6
91.6
156.4
142.7
95.3
156.4
121.6
91.6
149.0
149.5
150.4
150.0
149.9
150.2
‡
[I(2,6-F2C6H3)(2,4,6-F3C6H2)]
‡
[I(2,6-F2C6H3)2]
‡
‡
‡
[I(2,6-F2C6H3)(2-FC6H4)]
96.0
[I(2,6-F2C6H3)(3-FC6H4)]
106.1
[I(2,6-F2C6H3)(4-FC6H4)]
104.1
a Solvent CH3CN, external lock (CD3)2CO, ꢀ in ppm.

14
V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
Table 3
1
13Cf Hg-NMR chemical shifts of 2,6-difluorophenyl(fluorophenyl)iodine(III) tetrafluoroboratesa
ꢀ(C-1)
ꢀ(C-2,6)
ꢀ(C-3,5)
ꢀ(C-4)
ꢀ(C-10)
ꢀ(C-20)
ꢀ(C-03)
ꢀ(C-40)
ꢀ(C-50)
ꢀ(C-60)
‡
[I(2,6-F2C6H3)(C6F5)]
[I(2,6-F2C6H3)(2,4,6-F3C6H2)]
91.2
90.7
90.1
90.3
90.4
90.6
161.6
161.7
161.3
161.5
161.6
161.5
114.2
114.2
113.8
114.1
114.3
114.1
140.1
139.8
139.3
139.4
139.4
139.2
87.4
86.2
147.5
162.7
138.6
103.7
147.3
168.9
138.6
103.7
147.5
162.7
‡
‡
[I(2,6-F2C6H3)2]
‡
[I(2,6-F2C6H3)(2-FC6H4)]
[I(2,6-F2C6H3)(3-FC6H4)]
100.6
112.9
107.6
160.6
124.0
139.6
118.5
163.3
120.5
137.9
121.8
166.1
128.9
134.8
120.5
138.6
133.0
139.6
‡
‡
[I(2,6-F2C6H3)(4-FC6H4)]
Solvent CD3CN, ꢀ in ppm.
19
After a total reaction time of 48 h all volatile compounds
were distilled off in vacuo until a pale yellow residue
remained. The yields were quantitative. No melting was
observed up to the decomposition point of 3508C.
13Cf Fg-NMR (CD3CN): ꢀ: 161.9 (C-2,6), 157.8 (C=O),
139.8 (C-4), 116.6 (CF3), 114.3 (C-3,5), 90.6 (C-1).
Elemental analysis for C14H6F7IO2: [found (calculated)]
I: 27.68 (27.25)%; F, 28.18 (28.54)%.
1
The H- and 19F-NMR data for the aromatic rings were
identical with those of the corresponding tetra¯uoroborates.
The resonance of the CF3SO3 group was detected at
78.8 ppm in the 19F-NMR spectra and at 121.3 ppm
3.7. Synthesis of [I(2,6-F2C6H3)(2,4,6-
F3C6H2)][OCOCF3]
1
19
ꢀ Jꢀ F 13C† ˆ 319 Hz) in the 13C-NMR spectra.
0.38 g (0.83 mmol) [I(2,6-F2C6H3)(2,4,6-F3C6H2)][BF4]
was dissolved in 5 ml CH3CN and a solution of 0.14 ml
(0.80 mmol) (CH3)3SiOCOCF3 was added slowly at 08C.
After a reaction time of 4 days at room temperature the
solvent and other volatile products were distilled off. [I(2,6-
F2C6H3)(2,4,6-F3C6H2)][OCOCF3] was isolated as a white
solid.
3.6. Synthesis of [I(2,6-F2C6H3)2][OCOCF3]
0.97 g (2.2 mmol) [I(2,6-F2C6H3)2][BF4] were suspended
in 10 ml CH3CN at 08C. A precooled solution of 0.41 ml
(2.2 mmol) (CH3)3SiOCOCF3 in 10 ml CH3CN (08C) was
added dropwise and the mixture was stirred for 6 days at this
temperature. After distilling off all volatile components in
vacuo at room temperature [I(2,6-F2C6H3)2][OCOCF3] was
isolated as a white solid in 95% (0.98 g) yield.
Dec. >3008C. MS (EI, 20 eV, 1758C; m/e): 594 (1%,
[C24H8F9I] ),500(4%,[C18H5F8I] ),482(4%,[C18H6F7I] ),
‡
‡
‡
‡
‡
464 (1%, [C18H7F6I] ), 388 (2%, [C12H3F6I] ), 370 (5%,
‡
‡
‡
[C12H4F5I] ), 352(2%, [C12H5F4I] ), 338 (2%, [C18H8F6] ),
258 (42%, [C6H2F3I] ), 240 (35%, [C6H3F2I] ), 226 (2%,
‡ ‡
Dec. 2888C. MS (EI, 15 eV, 1758C; m/e): 576 (4%,
[C24H9F8I] ), 464 (9%, [C18H7F6I] ), 353 (16%,
‡
‡
‡ ‡ ‡
[F2C6H3OCOCF3] or[(F2C6H3)2] ),131(20%,[C6H2F3] ),
‡
‡
‡
‡
[C12H6F4I] ), 240 (100%, [C6H3F2I] ), 226 (4%,
‡
113 (20%, [F2C6H3] or [CF3CO2] ).
‡
‡
[F2C6H3OCOCF3] or [(F2C6H3)2] ), 113 (8%, [F2C6H3]
‡
19F-NMR (CH3CN): ꢀ: 76.6 (CF3), 91.9 (F-2,6 in
2,4,6-F3C6H2 group), 94.9 (F-2,6 in 2,6-F2C6H3), 95.6
(F-4 in 2,4,6-F3C6H2 group).
or [CF3CO2] ). 1H-NMR (CD3CN): ꢀ: 7.80 (H-4), 7.31 (H-
3,5). 19F-NMR (CD3CN): ꢀ: 75.9 (CF3), 94.5 (F-2,6).
Table 4
a
Melting points, decomposition points and experimental details for the synthesis of [I(2,6-F2C6H3)Arf][BF4] from 2,6-F2C6H3IF2 and B(Arf)3/BF3ÁO(CH3)2
Arf
C6F5
2,4,6-F3C6H2
2,6-F2C6H3
2-FC6H4
3-FC6H4
4-FC6H4
m (2,6-F2C6H3IF2)
m (B(Arf)3)
0.83 g [2.99]
0.51 g [1.00]
0.19 ml [2.07]
0.66 g (45%)
2728C
0.83 g [2.99]
0.40 g [0.99]
0.19 ml [2.07]
0.75 (55%)
0.83 g [2.99]
0.35 g [1.00]
0.19 ml [2.07]
1.12 g (85%)
0.83 g [2.99]
0.30 g [1.01]
0.19 ml [2.07]
0.88 g (70%)
1948C
0.83 g [2.99]
0.30 g [1.01]
0.19 ml [2.07]
0.63 g (50%)
1768C
0.83 g [2.99]
0.30 g [1.01]
0.19 ml [2.07]
0.59 g (47%)
1678C
m (BF3ÁO(CH3)2)
Yield
Melting point
Dec. point
3228C
2088C
2298C
2198C
2228C
2258C
aAmounts in mmol are given in square brackets. Yields are referenced to 2,6-F2C6H3IF2.

V. Padelidakis et al. / Journal of Fluorine Chemistry 99 (1999) 9±15
15
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[14] H. Butler, D. Naumann, W. Tyrra, Eur. J. Solid State Inorg. Chem. 29
(1992) 739.
Acknowledgements
Financial support by the Fonds der Chemischen Industrie
is gratefully acknowledged.
[15] H.J. Frohn, Nachr. Chem. Tech. Lab. 41 (1993) 956.
[16] H.J. Frohn, M. Giesen, A. Klose, A. Lewin, V.V. Bardin, J.
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[19] T. Umemoto, Y. Kuriu, H. Shuyama, O. Miyano, S.-I. Nakayama, J.
Fluorine Chem. 31 (1986) 37.
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