B.-J. Deelman et al.
SiC7H14CH3), 1.31 (m, SiCH2C6H12CH3), 7.38 (d, JH,H ϭ 7.8 Hz, 300.1 MHz): δ ϭ 0.93 (t, JH,H ϭ 7.4 Hz, CH2CH3), 1.38 (m,
FULL PAPER
3
3
3
2 Ar-Hm), 7.53 (d, JH,H ϭ 7.8 Hz, 2 Ar-Ho) ppm. 13C{1H}
CH2CH3), 1.96 (m, NCH2CH2), 2.15 (s, 12 H, ArCH3), 3.79 (s,
3
3
(CDCl3, 75.5 MHz): δ ϭ Ϫ2.8 (s), 0.7 (s), 14.4 (s), 15.9 (s), 22.9 NCH3), 4.16 (t, JH,H ϭ 7.5 Hz, NCH2), 6.75 (d, JH,H ϭ 7.5 Hz,
(s), 241. (s), 29.6 (s), 32.2 (s), 33.8 (s), 123.8 (s), 131.1 (s), 135.4 (s), 8 Ar-Hm), 7.25 (m, 8 Ar-Ho), 7.51 [s, C(5)H], 7.59 [s, C(4)H], 8.12
138.7 (s) ppm. C16H27Br (326.11): calcd. C 78.70, H 8.41; found C
78.56, H 8.35.
[s, C(2)H] ppm. 13C{1H} ([D6]acetone, 75.5 MHz): δ ϭ 13.0 (s),
19.3 (s), 20.6 (s), 32.1 (s), 35.9 (s), 49.5 (s), 122.5 (s), 123.9 (s),
126.2 (s), 129.5 (s), 136.3 (s), 161.2 (q, 1JBC ϭ 49.4 Hz, BϪC) ppm.
11B{1H} ([D6]acetone, 96.3 MHz): δ ϭ Ϫ12.79 (s) ppm. C36H43BN2
(514.35): calcd. C 84.03, H 8.42; found C 83.78, H 8.54.
Sodium
borate: tBuLi (12.6 mL, 1.5 in pentane, 20.2 mmol) was added to
4-bromo{dimethyl(3,3,3-trifluoropropyl)silyl}benzene (3.14 g,
Tetrakis{4-[dimethyl(3,3,3-trifluoropropyl)silyl]phenyl}-
1-Butyl-3-methylimidazolium Tetrakis{4-(trifluoromethyl)phenyl}-
borate (3): A mixture of Na[B{C6H4(CF3)-4}4] (3.87 g, 6.30 mmol)
and [BMIm]I (1.85 g, 6.93 mmol) was dissolved in CH2Cl2
(100 mL). After stirring for 2 d the mixture was poured into demin-
eralised water (40 mL) and the resulting mixture was washed with
demineralised water (5 ϫ 40 mL). The organic layer was then dried
with MgSO4, filtered and the solvent was removed in vacuo. The
resulting solid was washed with hexane (5 ϫ 100 mL) and dried in
vacuo, yielding a white solid (2.88 g; 63%). 1H NMR ([D6]acetone,
10.1 mmol) in Et2O (50 mL) at Ϫ78 °C. The mixture was allowed
to warm to room temperature over 16 h and then cooled to Ϫ78
°C with subsequent addition of BF3·Et2O (0.21 mL, 1.67 mmol).
This solution was then warmed to room temperature over 16 h,
poured into H2O and saturated with NaCl. After extraction with
Et2O (3 ϫ 50 mL) the combined organic layers were dried with
MgSO4 and the solvents removed in vacuo. The residue was taken
up in THF (25 mL), filtered through Celite and dried in vacuo,
yielding 1.33 g (83%) of a white solid. 1H NMR ([D4]MeOH,
300.1 MHz): δ ϭ 0.25 (s, 24 H, SiCH3), 0.89 (m, 8 H, SiCH2), 2.01
3
300.1 MHz): δ ϭ 0.95 (t, JH,H ϭ 7.4 Hz, CH2CH3), 1.38 (m,
3
3
CH2CH3), 1.96 (m, NCH2CH2), 4.08 (s, NCH3), 4.39 (t, JH,H
ϭ
(m, 8 H, CH2CF3), 7.17 (d, JH,H ϭ 7.9 Hz, 8 Ar-Hm), 7.37 (m, 8
3
Ar-Ho) ppm. 13C{1H} ([D4]MeOH, 75.5 MHz): δ ϭ Ϫ4.2 (s), 7.7
7.2 Hz, NCH2), 7.34 (d, JH,H ϭ 8.4 Hz, 8 Ar-Hm), 7.42 (m, 8 Ar-
Ho), 7.74 [s, C(5)H], 7.80 [s, C(4)H], 9.09 [s, C(2)H] ppm. 13C{1H}
([D6]acetone, 75.5 MHz): δ ϭ 13.0 (s), 19.3 (s), 32.1 (s), 36.1 (s),
(s), 28.5 (s), 128.3 (s), 128.3 (s), 130.2 (s), 130.7 (s), 135.9 (s), 166.5
1
(q, JBC ϭ 49.5 Hz, BϪC) ppm. C44H56BF12NaSi4 (958.33): calcd.
1
49.6 (s), 120.5 (s), 122.5 (s), 124.1 (q, JC,F ϭ 30.9 Hz, CF3), 125.0
C 55.10, H 5.89, Na 2.40; found C 54.84, H 5.85, Na 2.48.
1
(s), 131.3 (s), 135.9 (s), 136.7 (s), 167.4 (q, JBC ϭ 48.3 Hz, BϪC)
ppm. 11B{1H} ([D6]acetone, 96.3 MHz): δ ϭ Ϫ12.34 (s) ppm.
C36H31BF12N2 (730.24): calcd. C 59.20, H 4.28; found C 59.00,
H 4.04.
Sodium Tetrakis{4-[dimethyl(octyl)silyl]phenyl}borate: A procedure
similar
to that for sodium tetrakis{4-[dimethyl(3,3,3-
trifluoropropyl)silyl]phenyl}borate and 4-bromo{dimethyl(octyl)-
silyl}benzene (5.77 g, 21.5 mmol), tBuLi (23.5 mL, 1.5 in pen-
tane, 35.2 mmol) and BF3·Et2O (0.44 mL, 3.50 mmol) yielded a
brown oil. After washing with α,α,α-trifluorotoluene (3 ϫ 5 mL)
a white solid (2.42 g; 71%) was collected. 1H NMR ([D4]MeOH,
300.1 MHz): δ ϭ 0.21 (s, 24 H, SiCH3), 0.75 (s, 8 H, SiCH2), 0.92
(m, 12 H, C7H14CH3), 1.32 (m, 48 H, CH2C6H12CH3), 7.19 (d,
3JH,H ϭ 7.8 Hz, 8 Ar-Hm), 7.48 (m, 8 Ar-Ho) ppm. 13C{1H} ([D6]-
acetone, 75.5 MHz): δ ϭ Ϫ2.9 (s), 13.9 (s), 16.2 (s), 22.8 (s), 24.2
(s), 33.9 (s), 130.4 (s), 131.3 (s), 135.9 (s), 165.8 (q, 1JBC ϭ 49.5 Hz,
BϪC) ppm. C64H108BNaSi4 (1022.75): calcd. C 75.09, H 10.63;
found C 74.88, H 10.75.
1-Butyl-3-methylimidazolium Tetrakis{3,5-(trifluoromethyl)phenyl}-
borate (4): In a procedure similar to 3, Na[B{C6H3(CF3)2Ϫ3,5}4]
(1.40 g, 1.58 mmol) and [BMIm]I (0.39 g, 1.42 mmol) yielded a
white solid (1.31 g; 82%). 1H NMR ([D6]acetone, 300.1 MHz): δ ϭ
3
0.95 (t, JH,H ϭ 6.6 Hz, CH2CH3), 1.38 (m, CH2CH3), 1.97 (m,
3
NCH2CH2), 4.09 (s, NCH3), 4.40 (t, JH,H ϭ 7.4 Hz, NCH2), 7.33
(d, 8 Ar-Hm), 7.47 (m, 8 Ar-Ho), 7.76 [s, C(5)H], 7.81 [s, C(4)H],
9.18 [s, C(2)H] ppm. 13C ([D6]acetone, 75.5 MHz): δ ϭ 12.9 (s),
19.5 (s), 32.2 (s), 36.0 (s), 49.6 (s), 117.8 (s), 122.0 (s), 122.8 (s),
127.4 (s), 129.3 (q, 1JC,F ϭ 31.8 Hz, CF3), 134.8 (s), 136.8 (s), 162.5
(q, 1JBC ϭ 49.9 Hz, BϪC) ppm. 11B{1H} ([D6]acetone, 96.3 MHz):
δ ϭ Ϫ12.27 (s) ppm. C40H27BF24N2 (1002.19): calcd. C 47.93, H
2.71, I 0.00; found C, 47.93, H 2.79, I 0.00.
1-Butyl-3-methylimidazolium Tetraphenylborate (1):[8] In a pro-
cedure adapted from the literature (2.18 g, 6.37 mmol) Na[BPh4]
and (1.26 g, 5.79 mmol) [BMIm]Br were dissolved in H2O (30 mL)
and CH2Cl2 (30 mL). After stirring for 24 h, the layers were sepa-
rated and the CH2Cl2 layer was washed with water (2 ϫ 50 mL).
Drying in vacuo yielded a white solid (2.12 g; 80%). 1H NMR
1-Butyl-3-methylimidazolium
Tetrakis{4-(perfluorohexyl)phenyl}-
borate (5): In an analogous procedure to the synthesis of 3,
Na[B{C6H4(C6F13)-4}4] (2.39 g, 1.44 mmol) and [BMIm]I (0.42 g,
1.59 mmol) yielded a white solid (0.48 g; 20%). 1H NMR ([D6]ace-
3
3
([D6]acetone, 300.1 MHz): δ ϭ 0.92 (t, JH,H ϭ 7.4 Hz, CH2CH3),
tone, 300.1 MHz): δ ϭ 0.95 (t, JH,H ϭ 7.4 Hz, CH2CH3), 1.38 (m,
3
1.31 (m, CH2CH3), 1.79 (m, NCH2CH2), 3.75 (s, NCH3), 4.09 (t,
CH2CH3), 1.97 (m, NCH2CH2), 4.09 (s, NCH3), 4.40 (t, JH,H
ϭ
3
3JH,H ϭ 7.4 Hz, NCH2), 6.78 (t, JH,H ϭ 7.8 Hz, 4 Ar-Hp), 6.94 (t,
3
7.2 Hz, NCH2), 7.33 (d, JH,H ϭ 8.4 Hz, 8 Ar-Hm), 7.47 (m, 8 Ar-
Ho), 7.76 [s, C(5)H], 7.81 [s, C(4)H], 9.18 [s, C(2)H] ppm. 13C{1H}
([D6]acetone, 75.5 MHz): δ ϭ 12.8 (s), 19.3 (s), 32.1 (s), 36.0 (s),
3JH,H ϭ 7.5 Hz, 8 Ar-Hm), 7.36 (m, 8 Ar-Ho), 7.42 [s, C(5)H], 7.49
[s, C(4)H], 8.19 [s, C(2)H] ppm. 13C{1H} ([D6]acetone, 75.5 MHz):
δ ϭ 13.0 (s), 19.5 (s), 32.0 (s), 35.9 (s), 49.5 (s), 122.5 (s), 124.0 (s),
131.0 (s), 135.7 (s), 136.3 (s), 165.0 (q, 1JBC ϭ 49.5 Hz, BϪC) ppm.
11B{1H} ([D6]acetone, 96.3 MHz): δ ϭ Ϫ12.21 (s) ppm. C32H35BN2
(458.29): calcd. C 83.84, H 7.70; found C 83.17, H 7.59.
49.6 (s), 108.1 (m), 111.3 (m), 115.1 (m), 118.4 (m), 121.4 (m), 122.9
1
(m), 124.1 (s), 125.7 (s), 135.9 (s), 136.8 (s), 167.7 (q, JBC
ϭ
49.0 Hz, BϪC) ppm. 11B{1H} ([D6]acetone, 96.3 MHz): δ ϭ
Ϫ12.31 (s) ppm. C56H31BF52N2 (1730.17): calcd. C 41.67, H 3.45,
Cl 0.00; found C 41.88, H 3.61, Cl 0.00.
1-Butyl-3-methylimidazolium Tetrakis{4-(methyl)phenyl}borate (2):
A mixture of (0.79 g, 1.98 mmol) Na[B(C6H4Me-4)4] and (0.58 g, 1-Butyl-3-methylimidazolium
2.18 mmol) [BMIm]I was dissolved in H2O (20 mL). After stirring borate (6): mixture of Na[B{C6H4(SiMe3)-4}4] (1.48 g,
for 2 d the mixture was extracted with CH2Cl2 (2 ϫ 20 mL), dried 2.35 mmol) and [BMIm]Br (0.47 g, 2.14 mmol) was dissolved in
Tetrakis{4-(trimethylsilyl)phenyl}-
A
with MgSO4, filtered and all volatiles removed in vacuo. The re-
acetone (30 mL) and H2O (5 mL). After stirring for 24 h a white
solid was collected, taken up in acetone and filtered through Celite.
sulting solid was washed with hexane (2 ϫ 20 mL) and dried in
vacuo, yielding a white solid (0.64 g; 63%). 1H NMR ([D6]acetone, Slow evaporation of solvents yielded 0.61 g (38%) of a white crys-
2808
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2003, 2798Ϫ2811