Inorganic Chemistry
Article
Scheme 9
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1
C-2), 24.3 (q, J(C-1, F-3) = 8 Hz, C-1), 164.1 (d, J(C3, F3) = 259
Reaction of [C6F5Xe][BF4] with 4-FC6H4I in aHF. 4-Fluoroio-
dobenzene (49 mg, 0.21 mmol) was added to a solution of
[C6F5Xe][BF4] (82 mg, 0.21 mmol) in aHF (0.8 mL) and
subsequently the solution was stirred at ≈20 °C for 6 h. The 19F
spectrum (aHF, 0 °C) showed the complete conversion of
[C6F5Xe][BF4] under formation of [C6F5(4-FC6H4)I][BF4] and [(4-
FC6H4)2I][BF4] besides byproduct. The reaction mixture was
extracted with CCl3F (1 mL) and dried in vacuum. After an additional
extraction with CClF2CCl2F the residue was dried again and consisted
of [C6F5(4-FC6H4)I][BF4]25 (20% yield) and [(4-FC6H4)2I][BF4]26
(30% yield) (1H, 19F). The combined chlorofluorocarbon extracts
contained C6F5H, C6F5I, 1,4-C6F2H4 (yields 3%, 18%, and 6%,
respectively), 4-FC6H4I (conversion >90%), and probably, three
hexafluorobiphenyls (19F signals at −114.0 (1F, F1), −139.9 (2F, F-
2,6), −153.4 (1F, F-4), −161.0 ppm (2F, F-3,5); −118.0 (1F, F1),
−140.2 (2F, F-2,6), −153.5 (1F, F-4), −161.0, F-3,5); −118.7 (1F,
F1), −140.5 (2F, F-2,6), −153.6 (1F, F-4), −161.0 (2F, F3,5) (molar
ratio 1:2:2; total yield 10−15%).
Attempted Reaction of [C6F5Xe][BF4] with C6F5I in aHF.
Iodopentafluorobenzene (59 mg, 0.20 mmol) was added to a solution
of [C6F5Xe][BF4] (79 mg, 0.20 mmol) in aHF (0.6 mL), and the
emulsion was stirred at ≈20 °C for 24 h. The quantity of both reagents
did not change (19F).
Attempted Reaction of [C6F5Xe][BF4] with CF3CH2I in aHF.
CF3CH2I (46 mg, 0.22 mmol) was added to a solution of
[C6F5Xe][BF4] (79 mg, 0.20 mmol) in aHF (1 mL), and the solution
was stirred at ≈20 °C for 19 h without change of the quantities of both
reagents (19F).
Hz, C3), 135.1 (d, 3J(C5, F3) = 8 Hz, C5), 132.2 (d, 4J(C6, F3) = 4 Hz,
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C6), 123.4 (d, J(C2, F3) = 28 Hz, C2), 123.2 (d, J(C4, F3) = 21 Hz,
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C4), 110.7 (d, J(C1, F3) = 10 Hz, C1) ppm. 19F spectrum (aHF, 0
°C): δ(19F) = −51.7 (s, 3F, F-3), −100.8 (t, 6 Hz, d, 8 Hz, 1F, F3),
−147.8 (s, 4F, [BF4]−) ppm.
Reaction of [CF3CCXe][BF4] with C6F5I in aHF. A cold (−30
°C) solution of [CF3CCXe][BF4] (0.32 mmol) in aHF (0.51 mL)
was added in one portion to stirred neat C6F5I (−30 °C, 80 mg, 0.27
mmol). The reaction mixture was stirred in the closed trap at ≈20 °C
(bath) for 1 h. The 19F and 13C{19F} spectra showed the resonances of
[CF3CC(C6F5)I][BF4] and traces of C6F5I, while such of [CF3C
CXe][BF4] were absent. The volatiles were evaporated in vacuum at
≈20 °C and the residue was washed with CH2Cl2 and dried in vacuum.
[CF3CC(C6F5)I][BF4] (129 mg, 87%) was obtained as a white
solid.
[CF3CC(C6F5)I][BF4]. 13C{19F} spectrum (aHF, 0 °C): δ(13C) =
111.9 (C-3), 92.6 (C-2), 23.8 (C-1), 148.0 (C4), 146.6 (C2,6), 138.1
(C3,5), 82.8 (C1) ppm. 19F spectrum (aHF, 0 °C): δ(19F) = −52.0 (s,
3F, F-3), −117.3 (m, 2F, F2,6), −134.7 (tt, 4J(F4, F2) = 9 Hz, 3J(F4, F3)
= 19 Hz, 1F, F4), −152.2 (m, 2F, F3,5), −147.5 ppm (s, 4F, [BF4]−)
(cf., ref 24).
Reaction of [(CF3)2CFCCXe][BF4] with CF2CFI in aHF. A
cold (−40 °C) solution of [(CF3)2CFCCXe][BF4] (0.50 mmol) in
aHF (0.5 mL) was added in one portion to stirred neat CF2CFI
(−40 °C, 134 mg, 0.64 mmol). After the mixture was stirred at 0 °C
for 1 h and at ≈20 °C for 1.5 h, the conversion of [(CF3)2CFC
CXe][BF4] was ≈50% (19F). Full conversion was achieved by further
stirring at ≈20 °C (bath) overnight (≤12 h). After removing of the
volatiles in vacuum at ≈20 °C, the residue was washed with cold (4
°C) pentane (2x 2 mL) and dried in vacuum at 4 °C to yield
[(CF3)2CFCC(CF2CF)I][BF4] as a colorless viscous oil (116
mg, 47%). No decomposition of [(CF3)2CFCC(CF2CF)I][BF4]
occurred in aHF at ≈20 °C over 48 h (19F).
Reaction of [Cyclo-1,4-C6F7Xe][AsF6] with 4-FC6H4I in aHF. A
cold solution of [cyclo-1,4-C6F7Xe][AsF6] (94 mg, 0.18 mmol) in aHF
(0.6 mL) was added to a solution of 4-FC6H4I (51 mg, 0.23 mmol) in
aHF (0.5 mL) at 0 °C and the brown reaction mixture was stirred at 0
°C for 2 h and formed a two-phase system. The 19F spectrum of the
upper aHF phase at 0 °C showed the complete conversion of [cyclo-
1,4-C6F7Xe][AsF6] and the presence of [cyclo-1,4-C6F7(4-FC6H4)I]-
[AsF6] and [(4-FC6H4)2I][AsF6] besides byproduct. Further main-
taining of the dark mixture at ≈20 °C for 16 h did not affect on the
composition of products in the upper aHF phase (19F). After
extraction of the reaction mixture with CCl4 (1 mL), the aHF phase
was evaporated under reduced pressure and the resulting residue was
dissolved in MeCN (1 mL). The freshly prepared solution contained
[cyclo-1,4-C6F7(4-FC6H4)I][AsF6] (0.03 mmol, 17%) and [(4-
FC6H4)2I][AsF6] (0.07 mmol, 61%), besides signals of unknown
minor products. The carbon tetrachloride extract contained cyclo-1,4-
C6F7I, cyclo-1,4-C6F7H, and 1,4-C6F2H4.
[(CF3)2CFCC(CF2CF)I][BF4]. 11B spectrum (aHF, −20 °C):
δ(11B) = −2.2 ppm (s, [BF4]−). 13C{19F} spectrum (aHF, −20 °C):
δ(13C) = 119.3 (C-4), 90.2 (C-2), 85.6 (C-3), 30.6 (C-1), 154.8 (C2),
102.4 ppm (C1). 19F spectrum (aHF, −20 °C): δ(19F) = −74.0 (d,
3J(F-4, F-3) = 10 Hz, 6F, 2CF3), −169.2 (sept, J(F-3, F-4) = 10 Hz,
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1F, F-3), −71.8 (dd, J(F2trans, F2cis) = 16 Hz, J(F2trans, F1) = 71 Hz,
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1F, F2trans), −90.6 (dd, 2J(F2cis, F2trans) = 16 Hz, 3J(F2cis, F1) = 127 Hz,
1F, F2cis), −154.2 (dd, J(F1, F2trans) = 71 Hz, J(F1, F2cis) = 127 Hz,
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1F, F1), −147.8 ppm (s, 4F, [BF4]−).
Reaction of [CF3CCXe][BF4] with CF3CH2I in aHF. A cold
(−20 °C) solution of [CF3CCXe][BF4] (0.30 mmol) in aHF (0.5
mL) was added in one portion to stirred neat CF3CH2I (−20 °C, 77
mg, 0.36 mmol). After stirring at ≈15 °C (bath) for 1 h, the volatiles
were evaporated in vacuum at ≈20 °C. The residue was washed with
cold (5 °C) CH2Cl2 and dried in vacuum. [CF3CC(CF3CH2)I]-
[BF4] (116 mg, 99%) was obtained as a colorless oil and identified by
1H, 13C{19F}, 19F (aHF, 0 °C).24
[cyclo-1,4-C6F7(4-FC6H4)I][AsF6]. 19F spectrum (aHF, 10 °C):
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δ(19F) = −92.5 (ttd, J(F-6, F-3) = 4 Hz, J(F-6, F-2,4) = 10 Hz,
3J(F-6, F-5) = 21 Hz, 2F, F-6), −101.0 (m, 1F, F-2), −108.5 (tdt, 5J(F-
3, F-6) = 4 Hz, 4J(F-3, F-5) = 10 Hz, 3J(F-3, F-2,4) = 21 Hz, 2F, F-3),
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−147.1 (tt, J(F-5, F-3) = 11 Hz, J(F-5, F-6) = 21 Hz, 1F, F-5),
−152.4 (tt, 4J(F-4, F-6) = 10 Hz, 3J(F-4, F-3) = 19 Hz, 1F, F-4), −96.3
(tt, 4J(F4, H2,6) = 4 Hz, 3J(F4, H3,5) = 8 Hz, 1F, F4), −64 ppm (br, 6F,
[AsF6]−). 19F spectrum (MeCN): δ(19F) = −95.3 (ttd, 5J(F-6, F-3) = 4
Attempted reaction of [CF3CCXe][BF4] with C3F7I in aHF.
1-Iodoheptafluoropropane (88 mg, 0.30 mmol) was added in one
portion to a stirred cold (−78 °C) solution of [CF3CCXe][BF4]
(0.30 mmol) in aHF (0.5 mL). Following the reaction mixture was
stirred in the closed trap at ≈20 °C (bath) for 1 h. The 19F and
13C{19F} spectra showed only the presence of the starting reagents
[CF3CCXe][BF4] and C3F7I.
Hz, J(F-6, F-2,4) = 9 Hz, 3J(F-6, F-5) = 22 Hz, 2F, F-6), −94.1 (dtt,
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5J(F-2, F-5) = 3 Hz, 4J(F-2, F-6) = 10 Hz, 3J(F-2, F-3) = 24 Hz, 1F, F-
2), −110.5 (tddd, 5J(F-3, F-6) = 4 Hz, 4J(F-3, F-5) = 10 Hz, 3J(F-3, F-
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2) = 24 Hz, J(F-3, F-4) = 20 Hz, 2F, F-3), −148.9 (m, 1F, F-5),
−155.1 (dtt, 3J(F-4, F-5) = 4 Hz, J(F-4, F-6) = 10 Hz, 3J(F-4, F-3) =
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dx.doi.org/10.1021/ic202576v | Inorg. Chem. 2012, 51, 2616−2620