Full Paper
(170 mg, 0.63 mmol) was added, the mixture was slowly warmed
to RT and stirred for 2 h. The solvent was removed under vacuum,
and the residue was purified by column chromatography (silica
gel, 4:1 hexane/CH2Cl2) and subsequent precipitation from diethyl
ether by addition of methanol to provide 1 as a yellow solid
(303 mg, 87%).1H NMR (500 MHz, [D8]THF): d=7.51 (d, J=9 Hz,
2H), 7.39 (d, J=4 Hz, 1H), 7.33–7.32 (m, 2H), 7.27–7.23 (m, 5H),
7.09–7.07 (m, 4H), 7.03–7.00 (m, 4H), 6.81 (s, 4H), 2.27 (s, 6H),
2.13 ppm (s, 12H); 13C{1H} NMR (126 MHz, CD2Cl2): d=150.4, 149.1
(br), 148.2, 147.8, 145.1, 142.2, 141.5 (br), 141.2, 139.0, 135.8, 129.8,
128.6, 127.9, 126.8, 126.5, 125.9, 125.1, 123.8, 123.6, 123.5, 23.6,
21.4 ppm; 11B NMR (160 MHz, CD2Cl2): d=64 ppm (sbr); MS (EI+)
m/z: 658 [M]+; elemental analysis calcd (%) for C44H40BNS2: C 80.35,
H 6.13, N 2.13, S 9.75; found C 80.65, H 6.15, N 1.94, S 9.72.
(0.24 mL, 1.91 mmol) was added dropwise to the prepared
Grignard reagent at 08C (ice bath). The mixture was heated at
608C for 1 h, and then cooled to RT. Hexane (10 mL) was added to
the solution, the mixture was filtered and the filtrate was evaporat-
ed under vacuum to give a viscous oil. As-prepared (Tfp)2BF was
dissolved in THF (5.5 mL) without further purification. nBuLi (1.6m
in hexane, 0.18 mL, 0.29 mmol) was added to a THF (2 mL) solution
of TpaꢀThꢀTh (120 mg, 0.29 mmol) at ꢀ788C, and the mixture was
stirred at this temperature for 1 h. To this lithium reagent, a portion
of the prepared (Tfp)2BF solution (2 mL) was added. The mixture
was warmed to RT and stirred overnight. The solvent was removed
under vacuum, and the residue was purified by column chroma-
tography (silica gel, 3:1 hexane/CH2Cl2) and subsequent precipita-
tion from CH2Cl2 by addition of methanol to provide compound 3
as a yellow solid (198 mg, 65% based on TpaꢀThꢀTh). 1H NMR
(500 MHz, CD2Cl2): d=8.14 (s, 4H), 7.89 (s, 2H), 7.49–7.46 (m, 3H),
7.41 (d, J=4 Hz, 1H), 7.35 (s, 4H), 7.31(d, J=4 Hz, 1H), 7.30–7.27
(m, 4H), 7.20 (d, J=4 Hz, 1H), 7.12–7.10 (m, 4H), 7.08–7.03 (m, 4H),
2.34 ppm (s, 12H); 13C{1H} NMR (126 MHz, [D8]THF): d=152.7,
149.0, 148.4, 148.2 (br), 146.3, 145.4 (br), 144.5, 143.8, 142.8 (br),
139.4, 135.7, 132.7 (q, 2JCF =33 Hz), 130.2, 128.4, 128.2 (m), 127.7,
127.2, 127.1, 126.6, 125.6, 124.3, 124.2 (q, 1JCF =274 Hz), 124.2,
124.1, 121.7 (m), 24.0 ppm; 19F{1H} NMR (188 MHz, CD2Cl2): d=
ꢀ63.1 ppm (s, 12F); 11B NMR (160 MHz, CD2Cl2): ca. 66 ppm (weak
and broad); MS (EI+) m/z: 1054 [M]+; elemental analysis calcd (%)
for C58H40BF12NS2: C 66.10, H 3.83, N 1.33, S 6.09; found C 66.42, H
3.75, N 1.57, S 6.04.
TpaꢀThꢀThꢀB(Pfp)2 (2). THF (1 mL) and C2H4Br2 (4 drops) were
added sequentially to magnesium turnings (1.03 g, 42.9 mmol) at
RT, and the resulting mixture was stirred for 5 min. A solution of
PfpꢀBr (1.50 g, 4.29 mmol) in THF (4.3 mL) was prepared. A portion
(0.4 mL) of the PfpꢀBr solution was added at RT to the magnesium
turnings, and then the mixture was heated to 508C before the re-
maining PfpꢀBr solution was added dropwise. After addition, the
reaction mixture was heated at 608C for 20 min, before it was
cooled to RT and the solution was transferred to another flask by
syringe to leave the excess Mg as a solid residue. BF3·OEt2
(0.21 mL, 1.67 mmol) was added dropwise to the prepared
Grignard reagent at 08C (ice bath). The reaction mixture was
heated at 608C for 15 min and then cooled to RT. After the addi-
tion of hexane (10 mL), the mixture was filtered, and the filtrate
was evaporated under vacuum to give a viscous oil. As-prepared
(Pfp)2BF was dissolved in THF (3 mL) and used without further pu-
rification. nBuLi (1.6m in hexane, 0.45 mL, 0.72 mmol) was added
to a THF (5 mL) solution of TpaꢀThꢀTh (295 mg, 0.72 mmol) at
ꢀ788C, and the mixture was stirred at this temperature for 1 h.
The prepared lithium reagent was transferred to the prepared
(Pfp)2BF solution (08C) by cannula. The obtained mixture was
warmed to RT and stirred overnight. The solvent was removed
under vacuum, and the residue was purified by column chroma-
tography (silica gel, 4:1 hexane/CH2Cl2) and subsequent precipita-
tion from CH2Cl2 by addition of methanol to provide compound 2
as a yellow solid (300 mg, 43% based on TpaꢀThꢀTh). 1H NMR
(500 MHz, CD2Cl2): d=7.51 (d, J=4 Hz, 1H), 7.48 (d, J=9 Hz, 2H),
7.41 (d, J=4 Hz, 1H), 7.33 (d, J=4 Hz, 1H), 7.30–7.27 (m, 4H), 7.20
(d, J=4 Hz, 1H), 7.14 (s, 4H), 7.13–7.11 (m, 4H), 7.08–7.04 (m, 4H),
2.31 ppm (s, 12H); 13C{1H} NMR (126 MHz, CD2Cl2): d=152.1, 148.3,
147.7, 147.4 (br), 145.8, 145.7 (m, CF), 145.2 (br), 143.7 (m, CF),
143.7, 141.7 (br), 141.7 (m, CF), 139.6 (m, CF), 138.3 (dm, CF), 135.3,
129.8, 129.2, 127.7, 127.2, 127.1, 126.8, 126.2, 125.2, 123.8, 123.6,
123.5, 116.5 (m), 23.9 ppm; 19F{1H} NMR (188 MHz, CD2Cl2): d=
ꢀ143.5 (dd, J=23, 8 Hz, 4F), ꢀ156.9 (t, J=21 Hz, 2F), ꢀ163.2 to
ꢀ163.5 ppm (m, 4F); 11B NMR (160 MHz, CD2Cl2): d=65 ppm (sbr);
MS (EI+) m/z: 962 [M]+; elemental analysis calcd (%) for
C54H34BF10NS2: C 67.44, H 3.56, N 1.46, S 6.76; found C 67.71, H
3.20, N 1.56, S 6.67.
TpaꢀThꢀThꢀB(FMes)2 (4). nBuLi (2.5m in hexane, 0.16 mL,
0.40 mmol) was added to a THF (4 mL) solution of TpaꢀThꢀTh
(150 mg, 0.37 mmol) at ꢀ788C, and then the mixture was slowly
warmed to ꢀ258C during 1 h. After the solvent was removed
under vacuum, toluene (2 mL) was added to the residue at approx-
imately ꢀ258C. A toluene (5 mL) solution of (FMes)2BF (220 mg,
0.37 mmol) was added to the prepared lithium reagent, the reac-
tion mixture was warmed to RT and stirred overnight. The solvent
was removed under vacuum, and the residue was purified by
column chromatography (silica gel, 4:1 hexane/CH2Cl2) and subse-
quent crystallization from hexane at ꢀ308C to provide compound
1
4 as a red solid (40 mg, 11%). H NMR (500 MHz, [D8]THF): d=8.44
(s, 4H), 7.52 (d, J=9 Hz, 2H), 7.48 (d, J=4 Hz, 2H), 7.44 (d, J=4 Hz,
1H), 7.34 (d, J=4 Hz, 1H), 7.32 (d, J=4 Hz, 1H), 7.27–7.24 (m, 4H),
7.09–7.07 (m, 4H), 7.04–7.02 ppm (m, 4H); 13C{1H} NMR (126 MHz,
[D8]THF): d=154.8, 149.2, 148.3, 147.7, 146.4, 134.6, 133.9, 133.6,
130.2, 129.1, 128.1, 127.3, 126.5, 125.7, 124.9, 124.5, 124.3, 123.9,
122.7 ppm; 19F{1H} NMR (188 MHz, CD2Cl2, RT): d=ꢀ50.4 (sbr, 3F),
ꢀ52.1 (sbr, 3F), ꢀ56.5 (sbr, 6F), ꢀ63.4 ppm (s, 6F); 19F{1H} NMR
(188 MHz, CD2Cl2, 223 K): d=ꢀ50.0 (q, J=13 Hz, 3F), ꢀ51.8 (q, J=
11 Hz, 3F), ꢀ56.0 (q, J=11 Hz, 3F), ꢀ56.4 (q, J=13 Hz, 3F), ꢀ62.8
(s, 3F), ꢀ62.9 ppm (s, 3F); 11B NMR (160 MHz, [D8]THF): not ob-
served; MS (EI+) m/z: 981 [M]+; elemental analysis calcd (%) for
C44H22BF18NS2: C 53.84, H 2.26, N 1.43, S 6.53; found C 54.34, H
2.44, N 1.66, S 6.33.
TmjulꢀThꢀThꢀB(Pfp)2 (5). nBuLi (1.6m in hexane, 0.63 mL,
1.01 mmol) was added to a THF (2.3 mL) solution of TmjulꢀThꢀTh
(375 mg, 0.95 mmol) at ꢀ788C, and the mixture was stirred at this
temperature for 1 h. The prepared lithium reagent was transferred
to a THF solution of (Pfp)2BF at 08C, which was prepared using the
same method and in the same amount as that used in the synthe-
sis of 2. The mixture was warmed to RT and stirred overnight. The
solvent was removed under vacuum, and the residue was purified
by column chromatography (silica gel, 3:1 hexane/CH2Cl2) and sub-
sequent precipitation from CH2Cl2 by addition of methanol to pro-
vide compound 5 as a red solid (430 mg, 48% based on Tmjulꢀ
TpaꢀThꢀThꢀB(Tfp)2 (3). THF (1 mL) and C2H4Br2 (4 drops) were
added sequentially to magnesium turnings (909 mg, 37.9 mmol) at
RT, and the resulting mixture was stirred for 5 min. A solution of
TfpꢀBr (1.50 g, 3.79 mmol) in THF (5.70 mL) was prepared. A por-
tion (0.5 mL) of the TfpꢀBr solution was added at RT to the magne-
sium turnings, and then the mixture was heated to 508C before
the remaining solution was added dropwise. After addition, the re-
action mixture was heated at 608C for 30 min, before it was
cooled to RT and the solution was transferred to another flask by
syringe to leave the excess Mg as a solid residue. BF3·OEt2
Chem. Eur. J. 2014, 20, 1 – 15
11
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ