Explored routes to unknown polyfluoroorganyliodine hexafluorides, R FIF6

Article abstract of DOI:10.1016/j.jfluchem.2010.07.005

Two routes to R_FIF₆ compounds were investigated: (a) the substitution of F by R_F in IF₇ and (b) the fluorine addition to iodine in R_FIF₄ precursors. For route (a) the reagents C₆F₅SiMe₃, C₆F ₅SiF₃, [NMe₄][C₆F ₅SiF₄], C₆F₅BF₂, and 1,4-C₆F₄(BF₂)₂ were tested. C ₆F₅IF₄ and CF₃CH₂IF ₄ were used in route (b) and treated with the fluoro-oxidizers IF₇, [O₂][SbF₆]/KF, and K₂[NiF ₆]/KF. The observed sidestep reactions in case of routes (a) and (b) are discussed. Interaction of C₆F₅SiX₃ (X = Me, F), C₆F₅BF₂, 1,4-C₆F ₄(BF₂)₂ with IF₇ gave exclusively the corresponding ring fluorination products, perfluorinated cyclohexadiene and cyclohexene derivatives, whereas [NMe₄][C₆F ₅SiF₄] and IF₇ formed mixtures of C ₆F_nIF₄ and C₆F_nH compounds (n = 7 and 9). CF₃CH₂IF₄ was not reactive towards the fluoro-oxidizer IF₇, whereas C₆F ₅IF₄ formed C₆F_nIF₄ compounds (n = 7 and 9). C₆F₅IF₄ and CF ₃CH₂IF₄ were inert towards [O ₂][SbF₆] in anhydrous HF. CF₃CH ₂IF₄ underwent C-H fluorination and C-I bond cleavage when treated with K₂[NiF₆]/KF in HF. The fluorine addition property of IF₇ was independently demonstrated in case of perfluorohexenes. C₄F₉CFCF₂ and IF₇ underwent oxidative fluorine addition at -30 °C, and the isomers (CF ₃)₂CFCFCFCF₃ (cis and trans) formed very slowly perfluoroisohexanes even at 25 °C. The compatibility of IF₇ and selected organic solvents was investigated. The polyfluoroalkanes CF ₃CH₂CHF₂ (PFP), CF₃CH ₂CF₂CH₃ (PFB), and C₄F₉Br are inert towards iodine heptafluoride at 25 °C while CF₃CH ₂Br was slowly converted to CF₃CH₂F. Especially PFP and PFB are new suitable organic solvents for IF₇.

Full text of DOI:10.1016/j.jfluchem.2010.07.005

Journal of Fluorine Chemistry 131 (2010) 1000–1006
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Explored routes to unknown polyfluoroorganyliodine hexafluorides, RFIF6
b
Hermann-Josef Frohn a, , Vadim V. Bardin
*
a Inorganic Chemistry, University of Duisburg-Essen, Lotharstr. 1, D-47048 Duisburg, Germany
b N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, Acad. Lavrentjev Ave. 9, 630090 Novosibirsk, Russia
A R T I C L E I N F O
A B S T R A C T
Article history:
Two routes to RFIF6 compounds were investigated: (a) the substitution of F by RF in IF7 and (b) the
fluorine addition to iodine in RFIF4 precursors. For route (a) the reagents C6F5SiMe3, C6F5SiF3,
[NMe4][C6F5SiF4], C6F5BF2, and 1,4-C6F4(BF2)2 were tested. C6F5IF4 and CF3CH2IF4 were used in route (b)
and treated with the fluoro-oxidizers IF7, [O2][SbF6]/KF, and K2[NiF6]/KF. The observed sidestep reactions
in case of routes (a) and (b) are discussed. Interaction of C6F5SiX3 (X = Me, F), C6F5BF2, 1,4-C6F4(BF2)2 with
IF7 gave exclusively the corresponding ring fluorination products, perfluorinated cyclohexadiene and
cyclohexene derivatives, whereas [NMe4][C6F5SiF4] and IF7 formed mixtures of C6FnIF4 and C6FnH
compounds (n = 7 and 9). CF3CH2IF4 was not reactive towards the fluoro-oxidizer IF7, whereas C6F5IF4
formed C6FnIF4 compounds (n = 7 and 9). C6F5IF4 and CF3CH2IF4 were inert towards [O2][SbF6] in
anhydrous HF. CF3CH2IF4 underwent C–H fluorination and C–I bond cleavage when treated with
K2[NiF6]/KF in HF. The fluorine addition property of IF7 was independently demonstrated in case of
perfluorohexenes. C4F9CF55CF2 and IF7 underwent oxidative fluorine addition at ꢀ30 8C, and the isomers
(CF3)2CFCF55CFCF3 (cis and trans) formed very slowly perfluoroisohexanes even at 25 8C. The
compatibility of IF7 and selected organic solvents was investigated. The polyfluoroalkanes CF3CH2CHF2
(PFP), CF3CH2CF2CH3 (PFB), and C4F9Br are inert towards iodine heptafluoride at 25 8C while CF3CH2Br
was slowly converted to CF3CH2F. Especially PFP and PFB are new suitable organic solvents for IF7.
ß 2010 Elsevier B.V. All rights reserved.
Received 2 July 2010
Accepted 8 July 2010
Available online 15 July 2010
Keywords:
Iodine heptafluoride
Pentafluorophenyliodine tetrafluoride
1,1,1-Trifluoroethyliodine tetrafluoride
Pentafluorophenyldifluoroborane
Pentafluorophenyltrifluorosilane
Pentafluorophenyltrimethylsilane
Pentafluorophenyltetrafluorosilicate anion
NMR spectroscopy
1. Introduction
2. Results and discussion
Iodine heptafluoride belongs to the rare types of molecules with
a hepta-coordinated central atom. For the first time, it was
prepared by Ruff and Keim from the elements in 1930 [1]. Up to
date its reactivity is not studied comprehensively. In 1989 some
chemical, physical, and spectral (NMR, Raman, IR) data of IF7 were
briefly reviewed [2]. Furthermore fluoride donor/acceptor proper-
ties [3–5], the hydrolysis, and fluorine–oxygen substitution
reactions with MNO3 [3] were reported. The structural data of
IF7 were discussed in [6,7]. To our knowledge, the reactivity of IF7
towards organo compounds and the substitution of fluorine by
organyl groups were not investigated.
In the present paper we show the compatibility of selected
polyfluorinated alkanes towards iodine heptafluoride and their
potential as solvents for IF7. We report results of the attempted
syntheses of the hitherto unknown type of RFIF6 molecules by two
different reaction routes: (a) by F/RF substitution in IF7 and (b) by
fluorine addition to iodine in RFIF4 precursors with different fluoro-
oxidizers.
2.1. Suitable organic solvents for IF7 and compatibility of selected
polyfluoroalkanes towards IF7
Iodine heptafluoride is well soluble in 1,1,1,3,3-pentafluoropro-
pane (HFC-245fa) (PFP) (>1.3 mmol or >340 mg per mL at ꢀ70 8C)
as wellin 1,1,1,3,3-pentafluorobutane (Solkane1 365mfc)(PFB). The
colorless solutions could be stored in FEP traps at 25 8C over 40 h
without any attack on the polyfluoroalkanes. The inertness towards
strong fluoro-oxidizers combined with a wide range of the liquid
state of PFB (mp ꢀ36 8C, bp 40 8C) and PFP (mp ꢀ103 8C, bp 15 8C)
and a good solubility of many polyfluoroorgano compounds suggest
theuseofbothpolyfluoroalkanesassolventsforinvestigationsofthe
reactivity of IF7. The content of IF7 in solution was controlled by 19
F
NMR spectrometry at low temperature. The 19F NMR spectrum of
IF7 in PFP displayed a resonance at 171 ppm which showed a
temperature-depending reversible broadening from Dn1/
2 = 1180 Hz (ꢀ90 8C) to 1480 Hz (ꢀ70 8C), 5200 Hz (ꢀ40 8C), and
6700 Hz (0 8C). These data coincide with the reported spectra of IF7
in CCl3F (
liquid IF7 (
d
d
(F) = 173.5, Dn1/2 = 1150 Hz at ꢀ110 8C) [7] and of neat
(F) = 171, Dn1/2 = 4100 ꢁ 300 Hz at 27 8C) [8].
Iodine heptafluoride did also not react with C4F9Br in PFP (25 8C,
* Corresponding author. Tel.: +49 203 379 3310; fax: +49 203 379 2231.
E-mail address: h-j.frohn@uni-due.de (H.-J. Frohn).
24 h) and reacted very slowly with CF3CH2Br, where bromine
0022-1139/$ – see front matter ß 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.07.005

H.-J. Frohn, V.V. Bardin / Journal of Fluorine Chemistry 131 (2010) 1000–1006
1001
carries more partial negative charge, to give CF3CH2F (trace after
27 h at 25 8C). After 60 h at 25 8C the quantitative reduction of IF7
to IF5 and the formation of polyfluoroethanes CF3CH2F and
CF3CHF2 were observed.
ring too, but the perfluorinated cycloalkenyltrifluorosilanes 9, 10,
and 11 were not formed. Instead, the perfluorocycloalkenyliodine
tetrafluorides 14 and 15 were found together with 1-H-poly-
fluorocycloalkenes 12 and 13, the perfluorinated cycloalkenes 6
and 7, and iodine pentafluoride (Scheme 3).
2.2. Attempts to synthesize RFIF6 by F/RF substitution in IF7
Principally, the formation of 14 and 15 from C6F5IF6 cannot be
excluded, but it seems more likely that they were formed by
alternative routes. Thus, the fluorination of [C6F5SiF4]ꢀ by IF7 led to
[cyclo-C6FnSiF4]ꢀ (n = 7, 9) and IF5. IF5 can then react by two
channels. IF5 and [C6F5SiF4]ꢀ give C6F5IF4 [15] which can be
fluorinated by IF7 (see below) to 14 and 15 (Scheme 7).
Alternatively, compounds 14 and 15 can be produced from
[cyclo-C6FnSiF4]ꢀ and IF5. The remarkable quantity of hydrogen-
containing cycloalkenes 12 and 13 is explained by a transformation
of 14 and 15 under the influence of fluoride ions [16].
During the last decade we have successfully used pentafluoro-
phenyldifluoroborane (16) as a pentafluorophenyl transfer reagent
for the preparation of pentafluorophenyliodonium(III, V), penta-
fluorophenylbromonium(III) [17,18,14], and pentafluorophenyl-
xenonium(II, IV) [19] salts. Based on this experience borane 16
seemed to offer a promising route to first types of up to now
unknown organyliodine(VII) compounds. Thus we studied the
reaction of 16 with iodine heptafluoride. We have found that after
addition of 16 in PFP to an equimolar amount of IF7 in PFP at ꢀ60 8C
only ring fluorination resulted and no hint on C6F5IF6 was obtained
(Scheme 4). Besides IF5, heptafluorocyclohexa-1,3-dien-1-yldi-
fluoroborane (17), heptafluorocyclohexa-1,4-dien-1-yldifluoro-
borane (18), and nonafluorocyclohex-1-en-1-yldifluoroborane
(19), in addition to a significant amount of BF3, the perfluorinated
diene 6 and alkene 7 were formed. In contrast to the reaction with
[C6F5SiF4]ꢀ, perfluorocycloalkenyliodine tetrafluorides 20, 14, and
15 were not found in the reaction solution after several days at
25 8C. This fact allows to conclude that no slow substitution of the
BF2 group by IF4 proceeded as consecutive reaction between
perfluoroalkenyl(difluoro)boranes and IF5.
From our previous systematic investigations of F/RF substitu-
tion reactions in halogen fluorides it was known that BrF3 [9] and
BrF5 [10] reacted with C6F5SiMe3 in CH2Cl2 in the presence of the
base MeCN to give C6F5BrFn (n = 2, 4). Under similar conditions IF3
[9] and IF5 [11] showed no substitution. We have now found that
the addition of a pentafluorophenyltrimethylsilane (1) – MeCN
(1:3) solution in PFP to a solution of IF7 in PFP at ꢀ60 to ꢀ40 8C led
to the slow reduction of IF7 to IF5 and fluorine addition to the
pentafluorophenyl moiety giving heptafluorocyclohexa-1,4-dien-
1-yltrimethylsilane (2), nonafluorocyclohex-1-en-1-yltrimethylsi-
lane (3), nonafluorocyclohex-1-en-3-yltrimethylsilane (4), nona-
fluorocyclohex-1-en-4-yltrimethylsilane (5), octafluorocyclohexa-
1,4-diene (6), and decafluorocyclohex-1-ene (7), besides a trace of
Me3SiF (Scheme 1).
Pentafluorophenyltrifluorosilane (8) was a successful reagent
for F/C6F5 mono-substitution in IF3 [9], IF5 [11], BrF3 [12], and BrF5
[13] under formation of C6F5HalFnꢀ1 (n = 3, 5). In case of BrF3 we
were able to show that 8 can also form the di-substitution product
[(C6F5)2Br]+ in reactions with a 1:2 ratio at elevated temperatures
[14].
Stirring pentafluorophenyltrifluorosilane (8), MeCN, and iodine
heptafluoride (1:2:0.8) in a PFP solution at ꢀ70 to ꢀ40 8C for 1.5 h
did not lead to C6F5IF6. Instead, a mixture of IF7 and IF5 (1:2)
together with heptafluorocyclohexa-1,3-dien-1-yltrifluorosilane
(9), heptafluorocyclohexa-1,4-dien-1-yltrifluorosilane (10), nona-
fluorocyclohex-1-en-1-trifluorosilane (11), 1-H-heptafluorocyclo-
hexa-1,4-diene (12), perfluorinated cycloalkenes 6, 7, and SiF4 was
formed. Warming up to 0 8C resulted in the complete consumption
of IF7 (Scheme 2). The predominant reactivity of IF7 was again
fluorine addition across the C55C double bonds of the phenyl group.
Iodine heptafluoride and a suspension of [Me4N][C6F5SiF4] in
PFP reacted at ꢀ30 to 0 8C under fluorine addition to the aromatic
To reduce the probability of fluorine addition to the aromatic
moiety, we included tetrafluorophenylen-1,4-bis(difluoroborane)
(21) in our F/RF investigations. Borane 21 contains two strong
electron-withdrawing BF2 groups (sI(BF2) = 0.15, sR(BF2) = 0.30
[(Scheme_1)TD$FIG]
Scheme 1.
[(Scheme_2)TD$FIG]
Scheme 2.
[(Scheme_3)TD$FIG]
Scheme 3.

1002
[(Scheme_4)TD$FIG]
H.-J. Frohn, V.V. Bardin / Journal of Fluorine Chemistry 131 (2010) 1000–1006
Scheme 4.
[(Scheme_5)TD$FIG]
MeCN
C6F5SiF3 þ IF5 þ 2Py ꢀ! C6F5IF4 þ SiF4 ꢄ 2Py
(5)
20 ꢂC; 24 h
100%
2.3. Attempts to synthesize RFIF6 by fluorination of iodine in RFIF4
precursors
We have included C6F5IF4 and CF3CH2IF4 in reactions with
fluoro-oxidizers with the aim to obtain the corresponding RFIF6
molecules. The treatment of pentafluorophenyliodine tetrafluoride
(24) with IF7 (1 equiv.) in PFP at ꢀ60 to ꢀ30 8C did not result in
C6F5IF6 but fluorine addition across C55C bonds occurred under
formation of heptafluorocyclohexa-1,3-dien-1-yliodine tetrafluo-
ride (20), heptafluorocyclohexa-1,4-dien-1-yliodine tetrafluoride
(14), and nonafluorocyclohex-1-en-1-yliodine tetrafluoride (15)
(Scheme 7).
Scheme 5.
[20]). Nevertheless, after addition of an equimolar amount of 21 to
IF7 in PFP at ꢀ60 8C we have found again fluorine addition to the
double bonds instead of F/RF substitution. Hexafluorocyclohexa-
1,3-dienylen-1,4-bis(difluoroborane) (22) and hexafluorocyclo-
hexa-1,4-dienylen-1,4-bis(difluoroborane) (23) were formed in
quantitative yields (Scheme 5).
A similar ring fluorination of 24 was observed with XeF2 in the
presence of a Lewis acid [23]. Both results indicate (a) that the
electron-withdrawing effect of the IF4 group is not strong enough
to protect the C6F5 group against such strong fluoro-oxidizers or (b)
that the valence electron lone pair of iodine(V) needs a stronger
fluoro-oxidizer. If conclusion (b) is true, then this route can be
excluded for RFIF6 syntheses where RF contains a C–C multiple
bond.
In order to evaluate the influence of the oxidation number of
iodine on the preference of channel (a) or (b) in C6F5I starting
materials we performed the reaction of iodopentafluorobenzene
(25) (1.6 equiv.) with IF7 and observed 57% conversion of C6F5I to
pentafluorophenyliodine difluoride (26) and IF5 (Eq. (6)). No
addition of fluorine to the C55C double bond took place.
Under the action of a second equivalent of IF7, the conjugated
isomer 22 was converted into cycloalkenyldifluoroborane 19,
cycloalkene 7, and boron trifluoride (Scheme 6).
When the reaction solution was kept at 25 8C over a period of 4
days, 1,4-diene 23 isomerized to 1,3-diene 22.
Why did the pentafluorophenyl transfer not proceed in IF7? The
experimental facts with IF7 argue for a fast fluorine addition to the
aryl-transfer reagent and a low rate for the F/C6F5 substitution in
IF7. Indeed, we can deduce a slow F/C6F5 substitution in IF7 relative
to iodine(III) and iodine(V) fluorides based on the following
examples. The rate of F/C6F5 substitution in C6F5IFn with C6F5BF2 in
CH2Cl2 decreases from n = 2 [21] to n = 4 [22] (Eqs. (1) and (2)).
CH2CL2
C6F5IF2 þ C6F5BF220 ꢂꢀC!; 0:5 h ½ðC6F5Þ2Iꢃ½BF4ꢃ
(1)
(2)
93%
ꢂ
C6F5I þ < 1IF7PFP;ꢀꢀ40!to 0 C C6F5IF2 þIF5
(6)
25
26
CH2Cl2
C6F5IF4 þ C6F5BF216ꢀ20 ꢂC; 70 h ½ðC6F5Þ2IF2ꢃ½BF4ꢃ
ꢀ!
64%
In order to avoid the reaction channel of fluorine addition to
C55C bonds we investigated the reaction of CF3CH2IF4 with IF7. We
have found that IF7 and 2,2,2-trifluoroethyliodine tetrafluoride
(27) did not react in PFP even at 25 8C over 16 h (Eq. (7)). The
unexpected inertness of CF3CH2IF4 prompted us to exclude
perfluoroalkyliodine tetrafluorides with a more electron-deficient
iodine atom from our investigations with IF7.
A similar trend was observed for the F/C6F5 substitution in BrF3,
BrF5, and IF5 in reactions with silane 8. The reaction of BrF3 with
C6F5SiF3 in CCl3F was completed within 1 h [12] (Eq. (3)) whereas
the aryl transfer to BrF5 required the presence of MeCN and
occurred within 12 h [10,13] (Eq. (4)). The related reaction of IF5
needed the presence of the stronger base pyridine and more rigid
conditions [11] (Eq. (5)).
PFP; 25 ꢂ
CF3CH2IF4 þ IF7
ꢀ!C; 16 hno reaction
(7)
27
CCl3
F
C6F5SiF3 þ BrF3ꢀ5 to 0 ꢂC; < 1 h
ꢀ!
C6F5BrF2 þSiF4
(3)
(4)
47%
In addition to the fluoro-oxidizer IF7 we investigated selected
reactions with [O2][SbF6] and K2[NiF6] under different conditions.
C6F5IF4 showed no reactivity towards [O2][SbF6] in aHF till 0 8C
(Eq. (8)). The inertness of C6F5IF4 towards the one-electron-oxidizer
CCIF2CCIF2
C6F5SiF3 þ BrF5
ꢀ!; 4MeCN C6F5BrF4 þSiF4 ꢄ 2MeCN
0
ꢂC; 12 h
58%
[(Scheme_6)TD$FIG]
Scheme 6.

[
H.-J. Frohn, V.V. Bardin / Journal of Fluorine Chemistry 131 (2010) 1000–1006
1003
3. Experimental
3.1. General
The NMR spectra were recorded on a Bruker AVANCE 300
spectrometer (300.13 MHz, 1H; 282.40 MHz, 19F; 96.29 MHz, 11B;
75.47 MHz, 13C). The chemical shifts are referenced to TMS (1H,
13C), BF3ꢄOEt2/CDCl3 (15%, v/v) (11B), and CCl3F (19F, with C6F6 as
secondary reference (ꢀ162.9 ppm)), respectively. The composition
of reaction mixtures and the yields of products were determined
by 19F NMR spectroscopy using the internal integral standards
C6F6, C4F9Br, or PFB.
Scheme 7.
Scheme 8.
[(Scheme_8)TD$FIG]
Products cyclo-1,3-C6F7-1-IF4 (20), cyclo-1,4-C6F7-1-IF4 (14),
and cyclo-1-C6F9-1-IF4 (15) [23], cyclo-1,3-C6F7-1-SiF3 (9), cyclo-
1,4-C6F7-1-SiF3 (10), cyclo-1,4-C6F7-1-SiMe3 (2), cyclo-1-C6F9-1-
SiF3 (11), cyclo-1-H-1,4-C6F7 (12), cyclo-1,4-C6F8 (6), [26], cyclo-1-
C6F9-1-SiMe3 (3) [27], and cyclo-1-H-1-C6F9 (13) [28] were
identified by 19F NMR spectroscopy.
[O2]+ is in contrast to the easyoxidation of the parent aryl compound
C6F6 under formation of the radical cation [C6F6]+ꢅ [24].
aHF;ꢆ0 ꢂ
C6F5IF4 þ 2½O2ꢃ½SbF6ꢃ ꢀ! Cno reaction
(8)
1,1,1,3,3-Pentafluoropropane (PFP) (Honeywell), 1,1,1,3,3-pen-
tafluorobutane (PFB) (Solvay), and CCl3F (K11, Solvay) were
From the work of Bartlett [25] it was known that [O2][SbF6]
dissolved in ‘‘basic’’ aHF below ꢀ50 8C provides the strong radical
fluoro-oxidizer O2F with an O–F bond energy of ꢇ13 kcal/mol.
When we treated CF3CH2IF4 with [O2][SbF6]/KF/aHF from ꢀ65 to
24 8C no reaction proceeded (Eq. (9)).
˚
stored over molecular sieves 3 A before use. Boron trifluoride
(Air Liquide), C6F5I (Bristol Organics), CF3CH2I (30) (Acros),
(CF3)2CFCF55CFCF3 (31) (ABCR) were used as supplied. Acetonitrile
(Baker) and dichloromethane (Baker) were purified and dried as
described in Ref. [29]. Anhydrous HF (aHF) was stored over CoF3.
Compounds CF3CH2Br (32) [30], C4F9CF55CF2 [31], C6F5SiF3 (8) [32],
C6F5SiMe3 (1) [33], C6F5IF4 (24) [34], [Me4N]F [35], PFP solutions of
C6F5BF2 [18] and of 1,4-C6F4(BF2)2 [36] were prepared as described.
IF7 was obtained from E. Jacob and stored in a Monel cylinder with
a Monel valve, [O2][SbF6] from B. Mu¨ller, and K2[NiF6]ꢄKF from H.
Willner.
ꢂ
CF3CH2IF4 þ 2½O2ꢃ½SbF6ꢃ þ 2KFaHF;ꢀ6ꢀ5!to 24 Cno reaction
(9)
The same combination of reagents converted CF3CH2I at ꢀ65 to
0 8C partially into CF3CH2IF4 (Eq. (10)).
ꢂC
CF3CH2I þ 5½O2ꢃ½SbF6ꢃ þ > 5KF aHF;ꢀꢀ6!5 to 0 CF3CH2IF4
partial conversion
þ 5O2 þ 5K½SbF6ꢃ
(10)
All manipulations were performed in FEP (block copolymer of
tetrafluoroethylene and hexafluoropropylene) or PFA (block
copolymer of tetrafluoroethylene and perfluoroalkoxyethylene)
equipment under an atmosphere of dry argon.
Finally, we reacted CF3CH2IF4 with K2[NiF6] in ‘‘basic’’ aHF. At
0 8C we observed the splitting of the C–I bond by fluorination and
formation of CF3CH2F and IF5. In a smaller extent also one C–H
bond was fluorinated (formation of CF3CHF2) (Scheme 8).
3.2. Preparation of CF3CH2IF4
2.4. Verification of the fluorine addition property of IF7 exemplified by
(A) Xenon difluoride (352 mg, 2.08 mmol), PFB (2 mL) and
CF3CH2I (200 mg, 0.95 mmol) were loaded in a 11.7-mm i.d. PFA
trap equipped with a magnetic stir bar. The solution was cooled to
ꢀ10 8C and BF3 was bubbled under stirring at ꢀ10 8C for 2 min and
at 20 8C for 40 min. The 19F NMR spectrum showed the formation
of CF3CH2IF4. The signals of XeF2 and CF3CH2I were absent.
Volatiles were evaporated at 20 8C under reduced pressure to give
CF3CH2IF4 (216 mg, 0.76 mmol, 79%) (white solid).
using a ‘‘non’’ polarized C55C double bond
All aforementioned fluorine additions to the C6F5 moiety were
influenced by the substituent at carbon-1: SiF3, BF2, IF4 groups as
electron-withdrawing substituents or SiMe3 and SiF4ꢀ as electron-
pushing substituents. We have chosen two constitutional isomers
of perfluorohexene in order to test the fluorine addition property of
IF7 to a ‘‘non’’ polarized C55C bond.
(B) CF3CH2I (117 mg, 0.55 mmol) and aHF (2 mL) were loaded in
a 11.7-mm i.d. PFA trap equipped with a magnetic stir bar. The
emulsion was cooled to 0 8C before a solution of XeF2 (233 mg,
1.37 mmol) in aHF (0.5 mL) was added in portions. The mixture
was stirred at 10–12 8C for 15 min and the excess of XeF2 was
quenched by the addition of C6F6. All volatiles were removed at
20 8C in vacuum. The residue was washed with pentane and dried
in vacuum to give CF3CH2IF4 in >90% yield.
No reaction between iodine heptafluoride and perfluorohex-1-
ene (28) was detected in PFP at ꢀ60 8C within 2 h, but at ꢀ30 8C
fluorine addition across the terminal C55C bond took place forming
perfluorohexane (29) (Eq. (11)). Under the same conditions, the
isomer perfluoro-4-methylpent-2-ene (31) with an internal C55C
bond was not fluorinated by IF7. A slow conversion of both cis-31
and trans-31 to perfluoroisohexane (33) proceeded at 24 8C and
was completed after 60 h (Eq. (12)). It is noteworthy that during
the long-term reaction in a FEP trap the fluorine addition was
accompanied by the formation of minor by-products (CF3)2CFCOF,
CF3COF (derived from 31) and (CF3)2CO and C2F5COF (derived from
the isomer (CF3)2C55CFC2F5). Probably, the slow formation of
oxygen-containing products was caused by water vapor which
diffused through the 0.35 mm fluoropolymer wall.
CF3CH2IF4. 1H NMR (PFB, 24 8C):
d
4.86 (q 3J(H1, F2) = 9 Hz, 2H,
H1). 1H NMR (aHF, 0 8C): 4.90 (q 3J(H1, F2) = 9 Hz, 2H, H1). 19F NMR
d
(PFP, 24 8C):
d
ꢀ19.9 (t 3J(IF4, H1) = 5 Hz, q 4J(IF4, F2) = 9 Hz, 4F, IF4),
ꢀ59.6 (t 3J(F2, H1) = 9 Hz, quin 4J(F2, IF4) = 9 Hz, 3F, F2). 19F NMR
(aHF, 0 8C):
d
ꢀ23.2 (s, Dn1/2 = 47 Hz, 4F, IF4), ꢀ58.6 (t 3J(F2,
H1) = 9 Hz, 3F, F2). 13C{19F} NMR (PFB, 24 8C):
d
121.0 (t 2J(C-2,
H1) = 6 Hz, C-2), 75.4 (t 1J(C-1, H1) = 152 Hz, C-1).
PFP;ꢀ30 ꢂ
C4F9CF2¼CF2 þIF7
ꢀ!C; 2 h C6F14 þIF5
(11)
(12)
28
29
3.3. Reaction of IF7 with 2-bromo-1,1,1-trifluoroethane
PFP; 24 ꢂC; 60 h
A cold (ꢀ65 8C) solution of CF3CH2Br (0.10 mmol) in PFP
(0.15 mL) was added to a cold (ꢀ65 8C) solution of IF7 (0.10 mmol)
ðCF3Þ2CFCF¼CFCF3 þIF7
ꢀ!
ðCF3Þ2CFC3F7 þIF5
33
31ðcis:trans¼12:88Þ

1004
H.-J. Frohn, V.V. Bardin / Journal of Fluorine Chemistry 131 (2010) 1000–1006
in PFP (0.30 mL). The solution was stirred at ꢀ60 8C for 2 h, at 25 8C
for 16 h (without reaction, 19F NMR) and for additional 27 h (trace
of CF3CH2F). After 60 h at 25 8C the red solution contained IF5
(0.10 mmol), CF3CH2Br (0.01 mmol), CF3CH2F (0.08 mmol), and
CF3CHF2 (0.01 mmol) (PFB as internal integral standard, 19F NMR).
for 1 h. The 19F NMR spectrum (ꢀ60 8C) contained signals of IF5,
BF3, 6, 7, and broadened resonances of 17, 18, and 19 in the
molar ratio 200:40:3:20:4:49:7 (C4F9Br as internal integral
standard). Further stirring at 25 8C for 24 h led to the loss of BF3
whereas the quantities of the other products were not changed.
Now the fine structure of the 19F resonances of perfluorocy-
cloalkenyldifluoroboranes 17, 18, and 19 became available for
analysis.
3.4. Attempts to substitute fluorine by pentafluorophenyl groups in IF7
3.4.1. Reaction of IF7 with pentafluorophenyltrimethylsilane
Cold (ꢀ45 8C) solutions of CH3CN (15 mg, 0.36 mmol) and
C6F5SiMe3 (1) (29 mg, 0.12 mmol) in PFP (each 0.4 mL) were added
to a cold (ꢀ70 8C) solution of IF7 (0.10 mmol) in PFP (0.25 mL). The
solution was stirred for 0.5 h at ꢀ60 8C and at ꢀ40 8C. The 19F NMR
spectrum (ꢀ40 8C) showed signals of IF7 (too broad for integra-
tion), IF5, 2, 3, 6, 7, 4, 5 (189:45:17:2:4:15:21) and Me3SiF (trace).
Stirring at 0–6 8C for 13 h led to the complete reduction of IF7 to IF5
and the corresponding changes in the molar ratio of products: IF5,
2, 3, 6, 7, 4, 5, and Me3SiF (217:26:22:3:4:15:29:8).
cyclo-1,3-C6F7-1-BF2 (17). 19F NMR (PFP):
d
ꢀ74.3 (s, Dn1/2
=
72 Hz, BF2), ꢀ93.4 (d 3J(F2, F3) = 16 Hz, t 4J(F2, F6) = 16 Hz, 1F, F2),
ꢀ112.8 (m, d 4J(F6, F2) = 16 Hz, 2F, F6), ꢀ123.9 (m, 2F, F5), ꢀ147.1 (t
5J(F3, F6) = 5 Hz, d 3J(F3, F2) = 16 Hz, t 4J(F3, F5) = 19 Hz, 1F, F3),
ꢀ150.1 (m, t 3J(F4, F5) = 17 Hz, 1F, F4). 11B NMR (PFP):
d 21 (s, Dn1/
2 = 76 Hz, BF2).
cyclo-1-BF2-1,4-C6F7 (18). 19F NMR (PFP):
d
ꢀ74.3 (s, Dn1/2
=
72 Hz, 2F, BF2), ꢀ98.2 (t 5J(F6, F3) = 5 Hz, d 4J(F6, F2) = 11 Hz, d 4J(F6,
F4) = 11 Hz, d 3J(F6, F5) = 20 Hz, 2F, F6), ꢀ102.4 (t 4J(F2, F6) = 11 Hz, t
3J(F2, F3) = 22 Hz, 1F, F2), ꢀ112.3 (t 5J(F3, F6) = 4 Hz, d 3J(F3,
cyclo-1-C6F9-3-SiMe3 (4). 19F NMR (PFP):
d
ꢀ109.8 (d 2J(F6A
,
F2) = 22 Hz, 4J(F3, F5) = 11 Hz, 3J(F3, F4) = 19 Hz, 2F, F3),
d d
F6B) = 280 Hz, 1F, F6A), ꢀ115.2 (d 2J(F6B, F6A) = 280 Hz, 1F, F6B),
ꢀ150.9 (d 5J(F5, F2) = 2 Hz, d 3J(F5, F4) = 4 Hz, t 4J(F5, F3) = 11 Hz,
ꢀ122.4 (d 2J(F4A
,
F4B) = 270 Hz, 1F, F4A), ꢀ141.2 (d 2J(F4B
,
t
3J(F5, F6) = 20 Hz, 1F, F5), ꢀ158.1 (d 4J(F4, F2) = 2 Hz, d 3J(F4,
F4A) = 270 Hz, 1F, F4B), ꢀ126.7 (d 2J(F5A, F5B) = 280 Hz, 1F, F5A),
ꢀ128.0 (d 2J(F5B, F5A) = 280 Hz, 1F, F5B), ꢀ129.0 (d 3J(F2, F1) = 9 Hz,
F5) = 4 Hz, t 4J(F4, F6) = 11 Hz, t 3J(F4, F3) = 19 Hz, 1F, F4). 11B NMR
(PFP):
d 21.1 (s, Dn1/2 = 76 Hz, BF2).
d
4J(F2, F6A) = 12 Hz, d 3J(F2, F3) = 32 Hz, 1F, F2), ꢀ155.4 (d 3J(F1,
cyclo-1-BF2-1-C6F9 (19). 19F NMR (PFP),
d
ꢀ74.3 (s, Dn1/2
=
F2) = 9 Hz, d 4J(F1, F3) = 12 Hz, t 3J(F1, F6A,6B) = 19 Hz, 1F, F1), ꢀ186.8
72 Hz, 2F, BF2), ꢀ98.4 (m, 1F, F2), ꢀ103.8 (m, 2F, F6), ꢀ119.8 (m, d
(m, d 4J(F3, F1) = 12 Hz, d 3J(F3, F2) = 32 Hz, 1F, F3).
3J(F3, F2) = 22 Hz, 2F, F3), ꢀ133.5 (m, 2F, F4), ꢀ133.2 (m, 2F, F5). 11
B
cyclo-1-C6F9-4-SiMe3 (5). 19F NMR (PFP):
d
ꢀ105.8 (d 2J(F6A
,
,
,
NMR (PFP): d 21.1 (s, Dn1/2 = 76 Hz, BF2).
F6B) = 282 Hz, 1F, F6A), ꢀ126.1 (m, d 2J(F6B, F6A) = 282 Hz, d 4J(F6B
F2) = 15 Hz,
d
3J(F6B
,
F1) = 28 Hz, 1F, F6B), ꢀ99.7 (d 2J(F3A
3.4.5. Reaction of IF7 with tetrafluorophenylen-1,4-
bis(difluoroborane)
F3B) = 303 Hz, 1F, F3A), ꢀ110.2 (d 2J(F3B, F3A) = 303 Hz, 1F, F3B),
ꢀ112.5 (m, d 2J(F5A, F5B) = 288 Hz, 1F, F5A), ꢀ124.3 (m, d 2J(F5B
,
A cold (ꢀ65 8C) solution of 1,4-C6F4(BF2)2 (0.08 mmol) in PFP
(1 mL) was added to a cold (ꢀ65 8C) stirred solution of IF7
(0.08 mmol) in PFP (0.4 mL). The solution was stirred at ꢀ60 8C for
1 h. The 19F NMR spectrum (ꢀ60 8C) contained signals of IF5, 22,
and 23 in the molar ratio 100:30:60 (C4F9Br as internal integral
standard). A second portion of IF7 (0.08 mmol) in PFP (0.4 mL) was
added at ꢀ60 8C. After stirring for 1 h at ꢀ60 8C and at ꢀ40 8C, the
19F NMR spectrum (ꢀ40 8C) showed resonances of IF5, 23, 19, and 7
in the molar ratio 240:30:7:13. No remarkable changes were
observed in the 19F NMR spectrum of the solution after 9 h at 25 8C,
although in the 11B NMR spectra now BF3 (9.2 ppm) appeared. On
long standing at 25 8C (ꢈ4 days), 23 isomerized to 22 while the
other products remained unchanged.
F5A) = 288 Hz, 1F, F5B), ꢀ151.8 (m, d 4J(F2, F6A) = 9.5 Hz, d 4J(F2,
F6B) = 15 Hz, d 3J(F2, F3A) = 20 Hz, d 3J(F2, F3B) = 24 Hz, 1F, F2),
ꢀ200.1 (m, 1F, F4).
3.4.2. Reaction of IF7 with pentafluorophenyltrifluorosilane
A cold (ꢀ70 8C) solution of CH3CN (12 mg, 0.29 mmol) in PFP
(0.1 mL) and a cold (ꢀ40 8C) solution of C6F5SiF3 (8) (34 mg,
0.13 mmol) in PFP (0.2 mL) were added in sequence to a cold
(ꢀ70 8C) solution of IF7 (0.10 mmol) in PFP (0.25 mL). The solution
was stirred at ꢀ70 8C for 0.5 h and at ꢀ40 8C for 1 h. The 19F NMR
spectrum (ꢀ40 8C) showed signals of IF7 and IF5 (59:131), 9, 10, 11,
6, 7, 12, and SiF4 (12:62:12:1:8:5:7). Stirring at 0 8C for 15 h
resulted in the complete reduction of IF7 to IF5 accompanied by the
corresponding changes in the molar ratio of products: 9, 10, 11, 6,
7, 12, and SiF4 (0:36:36:1:9:3:9).
cyclo-1,3-C6F6-1,4-(BF2) (22). 19F NMR (PFP, ꢀ60 8C):
ꢀ75.1 (s,
d
Dn1/2 = 330 Hz, 4F, BF2), ꢀ96.3 (t 4J(F2, F6) and 4J(F3, F5) = 16 Hz, 2F,
F2,3), ꢀ113.8 (d 4J(F6, F2) and 4J(F5, F3) = 16 Hz, 4F, F5,6). 11B NMR
(PFP, ꢀ60 8C):
d 20.4 (s, Dn1/2 = 360 Hz, BF2).
3.4.3. Reaction of IF7 with [Me4N][C6F5SiF4]
cyclo-1,4-C6F6-1,4-(BF2) (23). 19F NMR (PFP, ꢀ60 8C):
ꢀ75.1 (s,
d
A cold (ꢀ35 8C) solution of C6F5SiF3 (40 mg, 0.157 mmol) in PFP
(0.3 mL) was added to a cold (ꢀ70 8C) solution of [Me4N]F (18 mg,
0.193 mmol) in PFP (1.5 mL). A white suspension was formed
which was stirred at ꢀ30 8C for 25 min before a cold (ꢀ35 8C)
solution of IF7 (0.158 mmol) in PFP (0.15 mL) was added in one
portion. The suspension was stirred at ꢀ30 8C for 1 h and at 0 8C for
2 h before the colorless mother liquor was decanted. The
precipitate (presumably, [Me4N]2[SiF6]) was washed with PFB
(1 mL). The 19F NMR spectrum (0 8C) of the combined PFB solutions
showed signals of 14, 15, 6, 7, 12, and 13 (molar ratio
9:13:15:18:27:18) and unknown non-aromatic perfluoro com-
pounds. Iodine heptafluoride was quantitatively converted into IF5
Dn1/2 = 330 Hz, 4F, BF2), ꢀ98.1 (t 4J(F2, F6) and 4J(F5, F3) = 11 Hz, t
3J(F2, F3) and 3J(F5, F6) = 22 Hz, 2F, F2,5), ꢀ99.0 (d 3J(F3, F2) and 3J(F6,
F5) = 22 Hz, d 4J(F3, F5) and 4J(F6, F2) = 11 Hz, 4F, F5,6). 11B NMR (PFP,
ꢀ60 8C):
d 20.4 (s, Dn1/2 = 360 Hz, BF2).
3.5. Attempts to fluorinate iodine in polyfluoroorganyliodine
compounds
3.5.1. Reaction of pentafluorophenyliodine tetrafluoride with IF7
A cold (ꢀ60 8C) solution of IF7 (0.15 mmol) in PFP (0.3 mL) was
added to a cold (ꢀ60 8C) stirred fine suspension of C6F5IF4 (24)
(54 mg, 0.145 mmol) in PFP (0.4 mL). The reaction mixture was
stirred at ꢀ60 to ꢀ20 8C with periodic control of composition by
19F NMR spectroscopy (PFB as internal integral standard). The
molar ratio of IF5:20:14:15:24 was 60:22:27:0:192 (20% conver-
sion, ꢀ60 8C, 1.5 h), 107:40:48:0:152 (36% conversion, ꢀ40 8C,
1 h), 177:63:78:4:90 (62% conversion, ꢀ40 8C, 3 h), and
270:88:115:14:16 (93% conversion, ꢀ40 to ꢀ30 8C, 12 h).
(
19F NMR).
3.4.4. Reaction of IF7 with pentafluorophenyldifluoroborane
A cold (ꢀ60 8C) solution of C6F5BF2 (0.12 mmol) in PFP
(0.25 mL) was added to a cold (ꢀ60 8C) stirred solution of IF7
(0.15 mmol) in PFP (0.3 mL). The solution was stirred at ꢀ60 8C

H.-J. Frohn, V.V. Bardin / Journal of Fluorine Chemistry 131 (2010) 1000–1006
1005
3.5.2. Reaction of iodopentafluorobenzene (excess) with IF7
reaction, 19F NMR). Further stirring at ꢀ30 8C for 2 h showed the
A cold (ꢀ50 8C) solution of IF7 (0.10 mmol) in PFP (0.40 mL) was
added to a cold (ꢀ45 8C) solution of C6F5I (48 mg, 0.163 mmol) in
PFP (0.20 mL). Immediately a white precipitate was formed. The
suspension was stirred at ꢀ40 8C for 40 min and at 0 8C for 1 h. The
mother liquor was decanted at 0 8C and the residue was dissolved
in cold (0 8C) MeCN (0.4 mL). The amount of C6F5IF2 (0.08 mmol),
IF5 (0.06 mmol), and C6F5I (0.06 mmol) was determined from both
solutions by 19F NMR (C6F6 as quantitative integral standard).
quantitative formation of IF5 and C6F14 (1:1, 19F NMR).
3.6.2. Reaction of perfluoro-4-methylpent-2-ene with IF7
A cold (ꢀ30 8C) solution of (CF3)2CFCF55CFCF3 (31) (cis:-
trans = 12:88) (0.10 mmol) in PFP (0.14 mL) was added to a cold
(ꢀ25 8C) solution of IF7 (0.10 mmol) in PFP (0.30 mL). The solution
was stirred at ꢀ30 8C for 2 h (no reaction, 19F NMR), at 24 8C for 1 h
(6% conversion of 31), 16 h (60% conversion of 31), and 27 h (74%
conversion of 31). After overall 60 h of reaction the solution
contained perfluoroisohexane and IF5 besides traces of 31,
(CF3)2CFCOF (34.2 (septet 4J(F1, CF3) = 6 Hz, d 3J(F1, F2) = 22 Hz,
1F, F1), ꢀ73.5 (d 3J(F3, F2) = 8 Hz, d 4J(CF3, F1) = 6 Hz, 6F, CF3),
ꢀ180.0 (septet 3J(F2, CF3) = 8 Hz, d 3J(F2, F1) = 22 Hz, 1F, F2) ppm (cf.
[37])) CF3COF (15.8 (q 3J(F1, F2) = 6 Hz, 1F, F1), ꢀ74.0 (d 3J(F2,
F1) = 6 Hz, 3F, F2) ppm (cf. [38]), (CF3)2CO (ꢀ86.0 (s) ppm (cf. [38]),)
and C2F5COF (24.8 (t 3J(F1, F2) = 9 Hz, q 4J(F1, F3) = 5 Hz, 1F, F1),
ꢀ82.5 (d 3J(F3, F1) = 5 Hz, t 3J(F3, F2) = 2 Hz, 3F, F3), ꢀ120.9 (q 3J(F2,
F3) = 2 Hz, d 3J(F2, F1) = 9 Hz, 2F, F2) (cf. [39])) (19F NMR).
3.5.3. Reaction of 2,2,2-trifluoroethyliodine tetrafluoride with IF7
A cold (0 8C) solution of CF3CH2IF4 (0.10 mmol) in PFB (0.12 mL)
was added to a cold (ꢀ30 8C) solution of IF7 (0.10 mmol) in PFP
(0.30 mL). After stirring at 25 8C for 16 h the solution showed no
reaction (19F NMR).
3.5.4. Reaction of pentafluorophenyliodine tetrafluoride with
[O2][SbF6]
Salt [O2][SbF6] (148 mg, 0.55 mmol) was added to the cold
(ꢀ65 8C) stirred suspension of C6F5IF4 (99 mg, 0.26 mmol) in aHF
(2 mL). The suspension was stirred at ꢀ30 8C (1 h) and at 0 8C (1 h).
A probe of the mother liquor showed only 19F NMR signals of
C6F5IF4 and aHF. The suspension was extracted with dichloro-
methane (1 mL) at 0 8C. The extract contained C6F5IF4 (nearly
quantitative recovery) (19F NMR).
(CF3)2CFC3F7 (33). 19F NMR (PFP, 0 8C):
d
ꢀ71.1 (d 6 Hz, t 8.5 Hz,
t 11 Hz, 6F, 2CF3), ꢀ79.8 (t 12 Hz, 3F, F5), ꢀ114.4 (m, 2F, F3), ꢀ124.1
(m, 2F, F4), ꢀ185.1 (m, 1F, F2). {lit.
d
ꢀ73 (2CF3), ꢀ82 (1CF3), ꢀ115
(2F, F3), ꢀ124 (2F, F4), ꢀ185 (1F, F2) [40]; ꢀ72.3 (2CF3), ꢀ81 (1CF3),
ꢀ115 (2F, F3), ꢀ125 (2F, F4), ꢀ185.5 (1F, F2) [41]}.
4. Conclusions
3.5.5. Reaction of 2,2,2-trifluoroethylliodine tetrafluoride with
[O2][SbF6] in basic HF
PFP and PFB are suitable solvents for IF7. They withstand the
oxidation property of IF7 and allow to investigate the reactivity of
IF7 towards organoelement and organo compounds. Two promis-
ing routes to hitherto unknown RFIF6 were investigated, but
without positive result concerning the goal. Instead, insight into
the reactivity of IF7 towards polyfluoroorganoelement compounds
was obtained. The substitution of F by C6F5 which was successful in
case of HalFn (Hal = Br, I; n = 3, 5) and XeFn (n = 2, 4) comes in case
of IF7 to a preparative limitation: the rate of substitution decreases
with increasing oxidation number (n) of iodine and parallel to n the
oxidation power of HalFn increases. Principally, the C6F5 group
offers relatively high nucleophilicity in combination with accept-
able resistance to oxidizers. But this group can undergo fluorine
addition to the C55C bonds under the action of IF7. The alternative
route to RFIF6 molecules, the fluorine addition to iodine in the
corresponding precursors C6F5IF4 and CF3CH2IF4 did not lead to the
target molecule RFIF6. [O2][SbF6]/HF is a no efficient fluoro-oxidizer
for C6F5IF4. IF7/PFP attacks the C55C bonds of C6F5IF4. CF3CH2IF4 is
inert to IF7 in PFP/PFB and [O2][SbF6] in aHF. Furthermore,
CF3CH2IF4 does not lead to the target molecule CF3CH2IF6 with
K2[NiF6] under increased oxidizing conditions in ‘‘basic’’ aHF.
A cold (ꢀ20 8C) solution of CF3CH2IF4 (0.24 mmol) and KF
(0.48 mmol) in aHF (2 mL) was added to a cold (ꢀ65 8C) stirred
suspension of [O2][SbF6] (117 mg, 0.43 mmol) in aHF (3 mL). The
suspension was warmed to 24 8C within 2 h and formed a colorless
solution which was stirred for further 24 h. The quantity of
CF3CH2IF4 did not change (19F NMR, 0 8C).
3.5.6. Reaction of 2,2,2-trifluoroethylliodine with [O2][SbF6] in basic
HF
A 11.7-mm i.d. PFA trap equipped with a magnetic stir bar was
charged with [O2][SbF6] (157 mg, 0.58 mmol) and cooled to 0 8C
before aHF (3 mL) was added. After cooling the solution to ꢀ65 8C a
cold (ꢀ55 8C) solution of KF (153 mg, 2.63 mmol) in aHF (0.6 mL)
was added. A suspension was formed which was stirred at ꢀ65 8C
for 40 min. CF3CH2I (24 mg, 0.11 mmol) was injected. The
suspension was stirred at ꢀ65 8C (40 min), ꢀ40 8C (15 min), and
ꢀ20 8C (20 min). When deposited in an ice bath the suspension
transformed into a colorless solution. After 1 h a probe contained
CF3CH2I and CF3CH2IF4 (78:22) (19F NMR, 0 8C).
3.5.7. Reaction of 2,2,2-trifluoroethylliodine tetrafluoride with
K2[NiF6] in basic HF
Acknowledgements
A cold (0 8C) solution of CF3CH2IF4 (0.2 mmol) in aHF (0.3 mL)
was added to a cold (0 8C) stirred deep-purple solution of K2[NiF6]
(80 mg, 0.31 mmol) and KF (18 mg, 0.31 mmol) in aHF (0.5 mL).
Immediately a pale-brown precipitate was formed. After centrifu-
gation at 0 8C, the colorless mother liquid was decanted. It
contained CF3CH2IF4, IF5, CF3CH2F, and CF3CHF2 (100:262:31:23)
We gratefully acknowledge financial support by the Deutsche
Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
We thank Prof. H. Willner, Prof. B. Mu¨ller, and Dr. E. Jacob for
providing us with chemicals.
(
19F NMR). The precipitate became greenish-yellow when residual
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