H.-J. Frohn, V. V. Bardin
FULL PAPER
135.1 (C-3 and C-4), 119.5 (C-5), 79.8 (d*, JC,Xe = 64 Hz, C-2),
6.9 (C-1) (the signal was too low in intensity to detect 1JC,Xe) ppm.
2
2
–60 °C): δ = 98.7 (d*, JC,Xe = 75 Hz, C-2), 28.7, 21.8, 20.5 (C-3,
C-4, C-5), 13.4 (C-6), –16.7 (d*, JC,Xe = 288 Hz, C-1) ppm. 19F
1
19F NMR (282.40 MHz, aHF, –60 °C): δ = –68.1 (d, 3JF,F = 12 Hz, NMR (282.40 MHz, CH2Cl2, –60 °C): δ = –143.0 (s, [BF4]–) ppm.
d, 4JF,F = 6 Hz, 3 F, F-5), –128.2 (d, q, 3JF,F = 12 Hz, 3JF,F = 3 Hz,
aHF (0.4 mL) was added to a solution of 6b in CH2Cl2 and stirred
at –45 °C for 10 min before the acidic phase was decanted.
5
3
4
d*, JF,Xe = 17 Hz, 1 F, F-4), –134.4 (d, JF,F = 3 Hz, q, JF,F
6 Hz, 1 F, F-3), –147.5 (s, 4 F, [BF4]–) ppm.
=
6b: 1H NMR (300.13 MHz, aHF, –30 °C): δ = 2.68 (t, 3JH,H = 7 Hz,
trans-4b: 11B NMR (96.29 MHz, aHF, –20 °C): δ = –1.3 (s, [BF4]–)
ppm. 13C{19F} NMR (75.46 MHz, aHF, –60 °C): δ = 148.0 and
3
3
2 H, 3-H), 1.66 (t, JH,H = 7 Hz, t, JH,H = 7 Hz, 2 H, 4-H), 1.46
3
(t, 3JH,H = 7 Hz, q, 3JH,H = 7 Hz, 2 H, H-5), 0.95 (t, JH,H = 7 Hz,
2
133.2 (C-3 and C-4), 116.3 (C-5), 79.8 (d*, JC,Xe = 64 Hz, C-2),
3 H, 6-H) ppm. 11B NMR (96.29 MHz, aHF, –30 °C): δ = –1.2 (s,
[BF4]–) ppm. 13C{1H} NMR (75.46 MHz, aHF, –30 °C): δ = 101.6
(d*, 2JC,Xe = 69 Hz, C-2), 29.0, 21.9, 20.1 (C-3, C-4, C-5), 12.0 (C-
1
7.9 (d*, JC,Xe = 332 Hz, C-1) ppm. 19F NMR (282.40 MHz,
3
4
aHF, –60 °C): δ = –67.9 (d, JF,F = 7 Hz, d, JF,F = 18 Hz, 3 F, F-
3
3
5), –150.0 (d, JF,F = 139 Hz, q, JF,F = 7 Hz, 1 F, F-4), –149.3 (d,
6), –24.0 (d*, JC,Xe = 264 Hz, C-1) ppm. 19F NMR (282.40 MHz,
1
4
4
3JF,F = 139 Hz, q, JF,F = 18 Hz, d*, JF,Xe = 6 Hz, 1 F, F-3),
aHF, –30 °C): δ = –147.8 (s, [BF4]–) ppm.
–147.5 (s, 4 F, [BF4]–) ppm.
B: A solution of C4H9CϵCBF2 (0.25 mmol) in PFP (0.7 mL) was
cooled to –70 °C and added in one portion to the cold (–70 °C)
suspension of xenon difluoride (54 mg, 0.32 mmol) in PFP
(0.2 mL). The brown reaction mixture was stirred at –65 °C for 1 h.
The NMR spectra of the suspension showed the total conversion
of 6a and the formation of 6b in Ͼ25% yield.
Pentafluorophenylethynylxenon(II) Tetrafluoroborate, [C6F5CϵCXe]-
[BF4], (5b)
A: A solution of C6F5CϵCBF2 (0.34 mmol) in PFP (0.9 mL) was
cooled to –55 °C, and xenon difluoride (50 mg, 0.29 mmol) was
added in one portion. The resulting suspension was stirred at –50
to –55 °C for 1 h. After centrifugation at –78 °C the brown mother
liquor was decanted at –45 °C. The residue was dried in vacuo
(0.13 hPa) at –45 °C, and pale brownish 5b was obtained (37 mg,
31%). The dissolution in aHF at –40 °C was accompanied by de-
composition of 5b. Total decomposition occurred within 30–50 min
(19F and 129Xe NMR).
1
6b: H NMR (300.13 MHz, PFP, –60 °C): δ = 1.58 (m, 2 H, 4-H),
1.42 (m, 2 H, 5-H), 0.91 (t, 3JH,H = 7 Hz, 3 H, 6-H) ppm (the signal
for 3-H overlapped with the resonance of PFP at 2.6 ppm). 11B
NMR (96.29 MHz, PFP, –60 °C): δ = –0.1 (s, [BF4]–) ppm. 13C{1H}
2
NMR (75.46 MHz, PFP, –60 °C): δ = 99.3 (d*, JC,Xe = 73 Hz, C-
1
2), 28.5, 21.4, 19.6 (C-3, C-4, C-5), 12.1 (C-6), –21.2 (d*, JC,Xe
=
B: A solution of C6F5CϵCBF2 (0.26 mmol) in CH2Cl2 (1.5 mL)
was cooled to –60 °C and xenon difluoride (38 mg, 0.22 mmol) was
added in one portion. The white suspension was stirred at –60 °C
for 1 h, and subsequently 5b (0.15 mmol, 68%) (19F NMR) was
extracted with cold (–65 °C) aHF (0.5 mL).
279 Hz, C-1) ppm. 19F NMR (282.40 MHz, PFP, –60 °C): δ =
–140.7 (s, [BF4]–) ppm. No changes were found in a solution of 6b
in CH2Cl2 after storage at –70 °C over 5 months. When 6b was
stored as aHF solution at 22 °C the content of 6b was reduced
from 95–100% (after 2 h) to 38% (after 22 h) to 10% (after 46 h).
1
5b: 11B NMR (96.29 MHz, aHF, –60 °C): δ = –1.7 (q, JB,F
=
3,3-Dimethylbut-1-ynylxenon(II)
Tetrafluoroborate,
[(CH3)3-
11 Hz, [BF4]–) ppm. 13C{19F} NMR (75.46 MHz, aHF, –60 °C): δ
= 149.5, 145.7, 137.9, 95.2 (C-2,6, C-4, C-3,5, and C-ipso, C6F5),
81.0 (d*, 2JC,Xe = 62 Hz, C-2), 0.6 (d*, 1JC,Xe = 308 Hz, C-1) ppm.
19F NMR (282.40 MHz, aHF, –60 °C): δ = –131.7 (m, 2 F, F-or-
CCϵCXe][BF4], (7b)
A: A cold (–60 °C) solution of (CH3)3CCϵCBF2 (0.44 mmol) in
PFP (1.7 mL) was added in one portion to the cold (–60 °C) stirred
suspension of xenon difluoride (69 mg, 0.40 mmol) in PFP
(0.1 mL). After 2 h, the reaction mixture was centrifuged at –78 °C
and subsequently the brown mother liquor was decanted at –65 °C.
The precipitate was dried at –60 °C in vacuo to give 7b (37 mg,
0.12 mmol). The mother liquor still contained borane 7a
(0.05 mmol) along with product 7b (0.15 mmol) (1H-, 11B-, 19F
NMR).
3
4
tho), –142.4 (t, JF,F = 19 Hz, t, JF,F = 6 Hz, 1 F, F-para), –159.0
(m, 2 F, F-meta), –148.1 (s, 4 F, [BF4]–) ppm.
The solution of 5b in aHF obtained as described under B showed
no significant decomposition at –60 °C over 13 h (19F-, 129Xe
NMR), but when the temperature was raised above –30 °C, 5b
quickly decomposed to give mainly cis-C6F5CF=CHF.[19]
cis-C6F5CF2=CHF1: 1H NMR (300.13 MHz, CDCl3, 24 °C): δ =
1
7b: H NMR (300.13 MHz, PFP, –50 °C): δ = 1.30 (s, CH3) ppm.
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3
6.80 (d, JH,F-1 = 71 Hz, d, JH,F-2 = 16 Hz) ppm. 19F NMR
11B NMR (96.29 MHz, PFP, –50 °C): δ = –1.4 (s, [BF4]–) ppm. 19F
NMR (282.40 MHz, PFP, –50 °C): δ = –138.9 (s, [BF4]–) ppm.
(282.40 MHz, CDCl3, 24 °C): δ = –135.9 (d, 3JF,H = 16 Hz, d, 3JF,F
= 15 Hz, t, JF,F-ortho = 15 Hz, 1 F, F-2), –138.0 (m, 2 F, F-ortho),
4
2
3
5
1
–149.1 (d, JF,H = 71 Hz, d, JF,F = 15 Hz, t, JF,F-ortho = 5, d,
7b: H NMR (300.13 MHz, aHF, –60 °C): δ = 1.26 (s, CH3) ppm.
7JF,F-para = 3 Hz, 1 F, F-1), –149.8 (t, JF,F = 21 Hz, 1 F, F-para),
3
1
11B NMR (96.29 MHz, aHF, –50 °C): δ = –1.2 (quintet, JB,F
=
10 Hz, [BF4]–) ppm. 13C{1H} NMR (75.46 MHz, aHF, –60 °C): δ
–160.4 (m, 2 F, F-meta) ppm.
2
= 107.0 (d*, JC,Xe = 76 Hz, C-2), 30.9 (C-3), 27.6 (CH3), –23.7
Hex-1-ynylxenon(II) Tetrafluoroborate, [C4H9CϵCXe][BF4], (6b)
(d*, JC,Xe = 267 Hz, C-1) ppm. 19F NMR (282.40 MHz, aHF,
1
A: A solution of C4H9CϵCBF2 (0.25 mmol) in CH2Cl2 (0.6 mL)
was cooled to –70 °C and added in one portion to the cold (–70 °C)
suspension of xenon difluoride (60 mg, 0.35 mmol) in CH2Cl2
(0.2 mL). The dark reaction mixture was stirred at –65 to –70 °C
for 1 h. The 1H- and 19F NMR spectra showed the quantitative
conversion of 6a into 6b.
–50 °C): δ = –148.0 (s, [BF4]–) ppm.
B: When a solution of 7b in PFP was warmed to 20 °C, it became
dark, and a black precipitate was formed within 5–10 min. The
decomposition of the colourless solution of 7b in aHF proceeded
slowly at 20 °C and led to a dark colouration. The intensity of the
129Xe NMR signal was also reduced to 80% (after 24 h) and then
to 11% (after 44 h).
1
3
6b: H NMR (300.13 MHz, CH2Cl2, –60 °C): δ = 2.59 (t, JH,H
=
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3
7 Hz, 2 H, 3-H), 1.55 (t, JH,H = 7 Hz, t, JH,H = 7 Hz, 2 H, 4-H),
3
3
3
1.35 (t, JH,H = 7 Hz, q, JH,H = 7 Hz, 2 H, 5-H), 0.87 (t, JH,H
=
7b: 1H NMR (300.13 MHz, CH2Cl2, –60 °C): δ = 1.28 (s, CH3)
ppm. 11B NMR (96.29 MHz, CH2Cl2, –60 °C): δ = –1.4 (s, [BF4]–)
7 Hz, 3 H, 6-H) ppm. 11B NMR (96.29 MHz, CH2Cl2, –60 °C): δ
= –1.4 (s, [BF4]–) ppm. 13C{1H} NMR (75.46 MHz, CH2Cl2, ppm. 13C{1H} NMR (75.46 MHz, CH2Cl2, –40 °C): δ = 105.7 (C-
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Eur. J. Inorg. Chem. 2006, 3948–3953