J. Harloff, M. Karsch, H. Lund, A. Schulz, A. Villinger
ARTICLE
7
5
29 (1), 719 (1), 699 (1), 679 (1), 651 (1), 634 (1), 619 (1), 607 (1), Synthesis of Na[B(O–C12
H
8
–CN)
] (1.5 g, 2.43 mmol, 1 equiv.) and HO–
–CN (0.95 g, 4.87 mmol, 2 equiv.) dissolved in CH CN (50 mL)
4
] (6): A Schlenk flask was loaded
–
1
51 (1), 498 (2), 434 (1), 410 (1), 386 (1), 267 (1), 244 (2) cm .
8 3
with Na[H–B(O–C12H –CN)
C
12
H
8
3
was added. A reflux condenser with a bubble counter was fixed on the
flask. The reaction mixture was heated to reflux for 7 h until the forma-
tion of hydrogen faded. The resulting suspension was filtered and the
solvent of the filtrate was removed in vacuo and dried at 100 °C. After
Synthesis of Na[B{O–C
nitrile (1.06 g, 8.67 mmol, 4.25 equiv.) was dissolved in thf (20 mL)
and added to a suspension of NaBH (66 mg, 1.75 mmol, 1 equiv.) in
thf (30 mL). The reaction mixture was heated to reflux for 3 h until
no further hydrogen evolution could be observed. The solvent was
removed in vacuo and CH CN (40 mL) was added. Heating to reflux
3
for further 4 h led to full exchange of the hydride. The excess of 5-
hydroxy-isophthalonitrile was separated from the reaction mixture by
6 3 2 4
H –(CN) } ] (4): 5-Hydroxy-isophthalo-
4
2
washing three times with Et O (50 mL) the product was dried at 70 °C
in vacuo for 3 h. Yield: 1.53 g (78%). TDec (onset): 301 °C. Anal.
1
calcd.% (found): C, 77.05 (76.56); H, 3.98 (4.29); N, 6.91 (6.73). H
6
NMR ([D ]DMSO, 300 MHz, 25 °C, ppm): δ = 7.69–7.81 (m, –CH–
CH–C–CN & –CH–C–CN, 16 H); 7.43–7.51 (m, –CH–CH–C–O–B, 8
crystallization from a cold concentrated CH
of the residual solution was removed in vacuo. Recrystallization from
a thf/CH Cl 2:1-mixture obtains solvated Na[B{O–C –(CN) ].
3
CN solution. The solvent
1
3
H); 7.16–7.23 (m, –CH–C–O–B, 8 H). C NMR ([D
6
]DMSO,
300 MHz, 25 °C, ppm): δ = 159.19 (s, –C–O–B, 4C); 145.14 (s, –C–
2
2
6
H
3
2 4
}
CH–CH–C–CN, 4C); 132.55 (s, –CH–C–CN, 8C); 127.43 (s, –CH–
CH–C–CN, 8C); 127.22 (s, –C–CH–CH–C–O–B, 4C); 126.26 (s,
–3
Removal of the guest molecules took place at 10 mbar and 150 °C.
Yield: 0.667 g (63%). TDec (onset): 318 °C. Anal. calcd.% (found):
–
CH–CH–C–O–B, 8C); 119.18 (s, –CH–C–O–B + –CN, 12C); 108.09
1
C, 63.39 (62.75); H, 1.99 (2.03); N, 18.48 (17.86). H NMR
11
(
s, –C–CN, 4C). B NMR ([D
6
]DMSO, 300 MHz, 25 °C, ppm): δ =
(
1
6
[D ]DMSO, 300 MHz, 25 °C, ppm): δ = 7.76 (t, NC–C–CH–C–CN,
2.87 (s). IR (ATR): = 2224 (m), 1597 (m), 1557 (w), 1536 (w), 1489
H, 4JH,H = 1.43 Hz); 7.70 (d, –CH–C–O, 2 H, JH,H = 1.43 Hz).
]DMSO, 300 MHz, 25 °C, ppm): δ = 157.1 (s, –C–O, 1C);
26.4 (s, NC–C–CH–C–CN, 1C); 123.6 (s, –CH–C–OH, 2C); 117.3
4
13
C
(
(
(
s), 1457 (w), 1421 (w), 1391 (w), 1309 (w), 1285 (m), 1249 (s), 1175
m), 1109 (m), 1026 (m), 1011 (m), 945 (vs), 934 (vs), 880 (m), 853
m), 821 (vs), 770 (m), 737 (m), 714 (m), 645 (m), 562 (s), 533 (vs)
NMR ([D
1
6
11
(s, –CN, 2C); 113.4 (s, –C–CN, 1C). B NMR ([D
6
]DMSO,
–
1
cm . Raman (1000 mW, 25 °C, 500 scans): = 2237 (2), 2219 (1),
3
1
1
5
00 MHz, 25 °C, ppm): δ = 2.34 (s). IR (ATR): = 3083 (w), 2235 (m),
1
5
615 (1), 1598 (10), 1326 (1), 1287 (4), 1179 (4), 911 (1), 784 (1),
20 (1), 414 (1), 398 (1), 304 (1), 207 (1), 105 (1) cm .
580 (s), 1553 (w), 1432 (s), 1321 (s), 1309 (s), 1255 (m), 1159 (s),
017 (vs), 997 (s), 984 (s), 942 (s), 921 (vs), 871 (s), 671 (s), 618 (m),
–
1
–1
76 (m) cm . Raman (1500 mW, 30 °C, 500 scans): = 3078 (1), 2238
Supporting Information (see footnote on the first page of this article):
Further details on the syntheses and characterizations of the starting
materials as well as compounds 3–6.
(10), 1588 (3), 1452 (1), 1439 (1), 1351 (3), 1331 (1), 1313 (1), 1255
(
5
1), 1125 (1), 1177 (2), 1030 (1), 997 (5), 983 (6), 932 (1), 614 (2),
73 (1), 549 (1), 521 (1), 467 (2), 440 (1), 379 (2), 207 (1) cm .
–
1
Acknowledgments
Synthesis of Na[H–B(O–C12
flask was loaded with NaBH
second one with HO–C12 –CN (1.35 g, 6.94 mmol, 4.1 equiv.). The
-Hydroxy-4Ј-cyano-1,1Ј-biphenyl was dissolved in thf (25 mL) and
this solution was added to the NaBH mixture. A reflux condenser
H
8
–CN)
3
] (5): In a drybox one Schlenk
4
(0.064 g, 1.69 mmol, 1 eqiuv.) and a
Financial support by the Deutsche Forschungsgemeinschaft (DFG) is
gratefully acknowledged. We are indebted to Fabian Reiß (University
Rostock) and Dr. Ronald Wustrack (University Rostock) for the mea-
surement of Raman spectra.
H
8
4
4
with a bubble counter was fixed on the flask and the reaction mixture
was heated to reflux for 4 h until no more hydrogen evolution was
observable. When the reaction was finished, a white precipitate was References
obtained, which was suspended in a yellow solution. The crude product
[
1] a) B. Chen, Y. Yang, F. Zapata, G. Lin, G. Qian, E. B. Lobkovsky,
was filtered off and washed two times with thf (10 mL). The pure
compound for analytical experiments was obtained after recrystalli-
zation from acetonitrile. Drying of the crystals at 10–3 mbar and 70 °C
Adv. Mater. 2007, 19, 1693–1696; b) S. M. Holmes, G. S. Girol-
ami, J. Am. Chem. Soc. 1999, 121, 5593–5594; c) V. Niel, J. M.
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for 1 h gave solvent-free Na[H–B(O–C12
H
8
–CN)
3
]. Yield: 0.669 g
(
(
3
64%). TDec (onset): 314 °C. Anal. calcd.% (found): C, 75.87
1
75.45); H, 4.08 (4.04); N, 6.45 (6.21). H NMR ([D
00 MHz, 25 °C, ppm): δ = 7.74–7.84 (m, –CH–CH–C–CN & –CH–
C–CN, 12 H); 7.50–7.57 (m, –CH–CH–C–O–B, 6 H); 6.97–7.04 (m,
6
]DMSO,
[2] a) B. F. Hoskins, R. Robson, J. Am. Chem. Soc. 1990, 112, 1546–
1554; b) L. G. Beauvais, J. R. Long, J. Am. Chem. Soc. 2002,
124, 12096–12097; c) B. F. Hoskins, R. Robson, J. Am. Chem.
CH–C–O–B, 6 H); 3.91 (br., –B–H, 1 H). 1 C NMR ([D
3
Soc. 1989, 111, 5962–5964; d) S. Shimomura, R. Matsuda, T.
Tsujino, T. Kawamura, S. Kitagawa, J. Am. Chem. Soc. 2006,
–
3
6
]DMSO,
00 MHz, 25 °C, ppm): δ = 161.46 (s, –C–O–B, 3C); 145.36 (s, –C–
128, 16416–16417; e) T. Küppers, E. Bernhardt, H. Willner, H. W.
CH–CH–C–CN, 3C); 132.60 (s, –CH–C–CN, 6C); 127.46 (s, –CH–
CH–C–CN, 6C); 126.46 (s, –C–CH–CH–C–O–B, 3C); 126.17 (s, –
CH–CH–C–O–B, 6C); 119.24 (s, –CN, 3C); 118.70 (s, –CH–C–O–B,
Rohm, M. Köckerling, Inorg. Chem. 2005, 44, 1015–1022.
3] M. D. Dembo, L. E. Dunaway, J. S. Jones, E. A. Lepekhina, S. M.
McCullough, J. L. Ming, X. Li, F. Baril-Robert, H. H. Patterson,
C. A. Bayse, R. D. Pike, Inorg. Chim. Acta 2010, 364, 102–114.
[
6
C); 107.92 (s, –C–CN, 3C). 11B NMR ([D
6
]DMSO, 300 MHz, 25 °C,
ppm): δ = 4.34 (br). IR (ATR): = 3034 (w), 2238 (m), 2224 (m), 1596
[4] a) Y. Sato, S. Ohkoshi, K. Arai, M. Tozawa, K. Hashimoto, J.
Am. Chem. Soc. 2003, 125, 14590–14595; b) S. Ohkoshi, K. Arai,
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(
(
(
(
s), 1558 (w), 1538 (w), 1520 (m), 1505 (w), 1489 (s), 1456 (w), 1424
w), 1403 (w), 1311 (w), 1260 (s), 1178 (m), 1145 (s), 1097 (s), 1023
m), 1004 (w), 903 (s), 866 (s), 853 (s), 817 (vs), 774 (s), 735 (s), 715
s), 682 (m), 665 (m), 649 (m), 632 (m), 561 (m), 548 (s), 531 (s)
46, 8123–8125.
[
5] a) G. J. Halder, C. J. Kepert, B. Moubaraki, K. S. Murray, J. D.
Cashion, Science 2002, 298, 1762–1765; b) K. Biradha, M. Fujita,
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P. J. Chupas, E. R. Maxey, J. W. Richardson, Chem. Commun.
2006, 4013–4015.
–1
cm . Raman (500 mW, 25 °C, 500 scans): = 2249 (2), 2233 (2), 1622
(1), 1609 (10), 1538 (1), 1326 (1), 1297 (3), 1290 (2), 1190 (4), 1155
(
7
1), 1103 (1), 1026 (1), 1013 (1), 930 (1), 880 (1), 821 (1), 793 (1),
45 (1), 645 (1), 426 (1), 410 (1) cm .
–1
1
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