5
0 h. The dark reaction mixture was cooled, the solvent re-
ities of the Regionale Rechenzentrum Erlangen (RRZE) is
gratefully acknowledged. We thank Prof. Tim Clark, Erlangen,
for discussions.
moved under reduced pressure and the black residue subjected
to preparative thin layer chromatography, eluting with 15%
dichloromethane/hexanes to give (1)-d
(
6
as yellow needles.
1.0 mg, 25%; mp ¼ 247 1C).
References
Method B. To a solution of hexakis(trimethylsilyl)-(1)
96 mg, 0.13 mmol) in dry CDCl (30 ml) was added trifluor-
1
2
Y. Haas and S. Zilberg, J. Am. Chem. Soc., 1995, 117, 5387.
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(
oacetic acid-d (4.0 ml). The reaction mixture was stirred over-
3
3
4
night at 25 1C under N and subsequently washed with water (2 ꢁ
2
5
was removed under reduced pressure to give (1)-d as a yellow
0 ml), brine (2 ꢁ 50 ml) and dried with MgSO
4
. The solvent
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6
powder. (36 mg, 90%; mp ¼ 247 1C; IR (KBr) n~ ¼ 3061 (vCH),
1 1
5
6
P. C. Hiberty and S. Shaik, Phys. Chem. Chem. Phys., 2004, 6, 224.
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ꢀ
1
2
(
265 (vCD), 1412, 1328, 889 (dCH), 603 (dCD) cm ; MS
70 eV) m/z (rel. intensity) 306 (M , 100); H NMR (500 MHz,
7
8
9
0
¨
Z. B. Maksic, D. Kovacek, M. Eckert-Maksic, M. Bockmann and
´ ´
1
3
1
C D ) d 6.97 (s, 6H); C{ H} NMR (100 MHz, CDCl ) d
6
6
3
M. Klessinger, J. Phys. Chem., 1995, 99, 6410.
1
48.5, 130.1, 128.2 (t, J ¼ 24 Hz), 119.7).
P. von R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao and N. J. R.
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H. Jiao, R. Puchta and N. J. R. van Eikema Hommes, Org.
Lett., 2001, 3, 2465.
Hexakis(trimethylsilylethynyl)benzene, (4)
1
A solution of hexabromobenzene (1 g, 1.8 mmol),
Pd(PPh Cl (110 mg, 0.16 mmol), CuI (30 mg, 0.16 mmol)
3
)
2
2
and trimethylsilylethyne (2 ml, 20 mmol) in 15 ml triethylamine
was heated in a glass bomb with a Teflon stopcock in an oil
bath at 120 1C. After 24 h, trimethylsilylethyne (1 ml, 10 mmol)
was added, followed by another 1 ml of trimethylsilylethyne
after an additional day. After 24 h, the solvent was removed
under reduced pressure. Column chromatography on silica
1
1
J. M. Schulman and R. L. Disch, J. Am. Chem. Soc., 1996, 118,
8470.
12 J. M. Schulman and R. L. Disch, J. Phys. Chem. A, 1997, 101, 5596.
1
3
J. M. Schulman, R. L. Disch, H. Jiao and P. von R. Schleyer,
J. Phys. Chem. A, 1998, 102, 8051.
J. M. Schulman and R. L. Disch, J. Phys. Chem. A, 2003, 107,
1
4
5
223–5227.
with hexane/CH Cl (85 : 15) gave (3) as brown crystals.
2
2
15 E. Steiner and P. W. Fowler, Int. J. Quantum Chem., 1996, 60, 609.
16 B. C. Berris, G. H. Hovakeemian and K. P. C. Vollhardt, J. Chem.
Soc., Chem. Commun., 1983, 502.
1 13
230 mg, 20%; H- and C NMR data were consistent with
(
those reported in the literature.)
5
3
1
7
M. Hirthammer and K. P. C. Vollhardt, J. Am. Chem. Soc., 1986,
08, 2481.
1
Triangular [4]phenylene-d , (1)-d
1
18 (a) L. Blanco, H. E. Helson, M. Hirthammer, H. Mestdagh, S.
Spyroudis and K. P. C. Vollhardt, Angew. Chem., 1987, 99, 1276;
2
12
A suspension of KF (470 mg, 8 mmol) in 10 ml dimethoxy-
ethane was stirred at room temperature for 5 min. D O (320 ml,
6 mmol) was added, and the suspension was again stirred for
(
b) L. Blanco, H. E. Helson, M. Hirthammer, H. Mestdagh, S.
2
Spyroudis and K. P. C. Vollhardt, Angew. Chem., Int. Ed. Engl.,
1987, 26, 1246.
(a) R. Diercks and K. P. C. Vollhardt, Angew. Chem., 1986, 98,
1
5
8
1
9
0
min. Then, a solution of (4) (70 mg, 0.1 mmol) and 16-crown-
(15 mg, 0.06 mmol) in 5 ml dimethoxyethane were added and
2
68; (b) R. Diercks and K. P. C. Vollhardt, Angew. Chem., Int. Ed.
Engl., 1986, 25, 266.
the pale yellow solution removed from the solid KF ꢃ 2D O
2
2
R. Diercks and K. P. C. Vollhardt, J. Am. Chem. Soc., 1986, 108,
3
after 15 min via a syringe. This solution was mixed with
CpCo(CO)2 (20 ml, 0.15 mmol) and injected over 8 h to
150.
21 R. H. Schmidt-Radde and K. P. C. Vollhardt, J. Am. Chem. Soc.,
1992, 114, 9713.
1
0 ml of boiling bis(trimethylsilyl)ethyne. During the addition,
2
2
(a) R. Boese, A. J. Matzger, D. L. Mohler and K. P. C. Vollhardt,
Angew. Chem., 1995, 107, 1630; (b) R. Boese, A. J. Matzger, D. L.
Mohler and K. P. C. Vollhardt, Angew. Chem., Int. Ed. Engl.,
the reaction mixture was irradiated with a slide projector lamp.
Heating and irradiation were continued overnight. Dimethox-
yethane was removed by rotary evaporation, and the bis(tri-
methylsilyl)ethyne was recovered by vacuum transfer. The
residue was purified by column chromatography on silica with
1
995, 34, 1478.
2
3
(a) C. Eickmeier, D. Holmes, H. Junga, A. J. Matzger, F.
Scherhag, M. Shim and K. P. C. Vollhardt, Angew. Chem.,
1999, 111, 856; (b) C. Eickmeier, D. Holmes, H. Junga, A. J.
Matzger, F. Scherhag, M. Shim and K. P. C. Vollhardt, Angew.
Chem., Int. Ed., 1999, 38, 800.
hexane/CH
a yellow oil.
The crude hexakis(trimethylsilyl)-(1)-d
2
Cl
2
(85 : 15) to give hexakis(trimethylsilyl)-(1)-d
6
as
6
was dissolved in a
2
4
5
A. Schleifenbaum, N. Feeder and K. P. C. Vollhardt, Tetrahedron
Lett., 2001, 42, 7329.
mixture of trifluoroacetic acid-d (1 ml, 170 mmol) and 6 ml
chloroform and the solution was stirred for 24 h at room
temperature. The volatiles were removed by vacuum transfer.
Column chromatography of the residue on silica with hexane/
CH Cl (85 : 15) and recrystallization from hexanes gave (1)-d
12
2
D. T.-Y. Bong, L. Gentric, D. Holmes, A. J. Matzger, F. Scherhag
and K. P. C. Vollhardt, Chem. Commun., 2002, 278.
26 P. I. Dosa, G. D. Whitener, K. P. C. Vollhardt, A. D. Bond and S.
J. Teat, Org. Lett., 2002, 4, 2075.
2
2
2
7
(a) S. Han, D. R. Anderson, A. D. Bond, H. V. Chu, R. L. Disch,
D. Holmes, J. M. Schulman, S. J. Teat, K. P. C. Vollhardt and G.
D. Whitener, Angew. Chem., 2002, 114, 3361; (b) S. Han, D. R.
Anderson, A. D. Bond, H. V. Chu, R. L. Disch, D. Holmes, J. M.
Schulman, S. J. Teat, K. P. C. Vollhardt and G. D. Whitener,
Angew. Chem., Int. Ed., 2002, 41, 3227.
as yellow needles. (6 mg, 18%; D-incorporation B98% by
ꢀ
1
mass spectrometry; IR (CsI) n~ ¼ 2289 (vCD), 1290, 582 cm
1
dCD); MS (70 eV) m/z (rel. intensity) 312 (M , 100).)
(
2
8
(a) S. Han, A. D. Bond, R. L. Disch, D. Holmes, J. M. Schulman,
S. J. Teat, K. P. C. Vollhardt and G. D. Whitener, Angew. Chem.,
2002, 114, 3357; (b) S. Han, A. D. Bond, R. L. Disch, D. Holmes,
J. M. Schulman, S. J. Teat, K. P. C. Vollhardt and G. D.
Whitener, Angew. Chem., Int. Ed., 2002, 41, 3223.
D. L. Mohler, K. C. P. Vollhardt and S. Wolff, Angew. Chem., Int.
Ed., 1995, 34, 563.
H.-D. Beckhaus, R. Faust, A. J. Matzger, D. L. Mohler, D. W.
Acknowledgements
This work was funded by the Fonds der Chemischen Industrie,
NSF (CHE-0071887), the Deutscher Akademischer Aus-
tauschdienst (D/0103669), and the EU-Access to Research
Infrastructures Programme (HPRI-CT-1999-00064). The Cen-
ter for New Directions in Organic Synthesis is supported by
Bristol–Myers Squibb as a Sponsoring Member and Novartis
as a Supporting Member. The use of the computational facil-
2
9
0
3
¨
Rogers, C. Ruchardt, K. P. C. Vollhardt and S. Wolff, J. Am.
Chem. Soc., 2000, 122, 7819.
5
482
P h y s . C h e m . C h e m . P h y s . , 2 0 0 4 , 6 , 5 4 7 6 – 5 4 8 3
T h i s j o u r n a l i s & T h e O w n e r S o c i e t i e s 2 0 0 4