C. Mechtler et al. / Journal of Organometallic Chemistry 691 (2006) 150–158
157
123.8, 116.5, 108.2, 3.8 ppm. 29Si NMR (THF/C6D6)
d = À7.3, À154.8 ppm.
272831 for 5, and 272832 for 6. Copies of the data can
be obtained free of charge on application to The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:
(internat.) +44 1223 336 033; e-mail: deposit@chemcrys.
cam.ac.uk).
4.6.2. 1,3-Bis[(bis(trimethylsilyl)silyl)ethynyl]benzene-
dipotassium (6a)
1H NMR (C6D6, THF, THF-d8) d = 7.24 (m, 1H), 7.03
(d, 2H, J = 7.4 Hz), 6.87 (t, 1H, J = 7.4 Hz), 0.58 (s, 36H)
ppm. 13C NMR (C6D6, THF, THF-d8) d 130.9, 130.3,
127.7, 126.3, 116.0, 107.9, 3.8 ppm. 29Si NMR (THF/
C6D6) d = À7.3, À155.3 ppm.
Acknowledgements
This study was carried out within the START project
Chiral polysilanes (Y120) funded by the Austrian ministry
of education, science and culture.
4.6.3. 1,3,5-Tris[(bis(trimethylsilyl)silyl)ethynyl]benzene-
tripotassium (7a)
References
1H NMR (C6D6, THF, THF-d8) d = 7.10 (s, 3H), 0.56
(s, 54H), 0.24 (s, 36H) ppm. 13C NMR (C6D6, THF,
THF-d8) d = 127.2, 125.3, 114.3, 107.4, 3.8 ppm. 29Si
NMR (THF/C6D6) d = À7.7, À155.3 ppm.
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benzene (5b)
To dimethylsulfate (0.26 mmol) in diethylether (3 mL)
the dipotassium compound 5a (0.09 mmol) in THF
(2 mL) was added at 0 ꢁC. The dark red color disappeared
immediately. The solution was stirred for 2 h at room tem-
perature before it was subjected to an extractive work-up.
(b) R. Fischer, D. Frank, W. Gaderbauer, C. Kayser, C. Mechtler, J.
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1
A colorless oil of 7 (42 mg, 99%) was obtained. H NMR
[3] C. Mechtler, M. Zirngast, J. Baumgartner, C. Marschner, Eur. J.
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[4] For a recent review concerning the state of polysilanes dendrimers,
see: J.B. Lambert, J.L. Pflug, H.W. Wu, X.Y. Liu, J. Organomet.
Chem. 685 (2003) 113–121.
(C6D6) d = 7.22 (s, 4H), 0.34 (s, 3H), 0.24 (s, 36H) ppm.
13C NMR (C6D6) d = 132.2, 131.9, 109.0, 93.5, À1.4,
À7.9 ppm. 29Si NMR (C6D6) d = À15.3, À64.3 ppm.
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4.6.5. 1,3-Bis[(bis(trimethylsilyl)methylsilyl)ethynyl]-
benzene (6b)
Angew. Chem., Int. Ed. Engl. 34 (1995) 98–99;
(b) A. Sekiguchi, M. Nanjio, C. Kabuto, H. Sakurai, J. Am. Chem.
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615–625;
Similar procedure as for compound 5b using 6a
(0.09 mmol) and dimethylsulfate (0.26 mmol). Compound
6b (43 mg, 100%) was obtained as a colorless oil. 1H
NMR (C6D6) d = 7.75 (t, 1H, J = 1.6 Hz), 7.25 (dd, 2H,
J = 1.6; 7.8 Hz), 6.67 (t, 1H, J = 7.8 Hz), 0.32 (s, 9H),
0.23 (s, 18H), 0,22 (s, 18H) ppm. 13C NMR (C6D6)
d = 135.5, 131.6, 128.6, 124.6, 108.4, 92.2, À1.5,
À7.9 ppm. 29Si NMR (C6D6) d = À15.3, À64.3 ppm.
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benzene (7b)
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Similar procedure as for compound 5b using 7a
(0.06 mmol) and dimethylsulfate (0.26 mmol). Compound
7b (44 mg, 100%) was obtained as a colorless oil. 1H
NMR (C6D6) d = 7.67 (s, 3H), 0.21 (s, 9H), 0.20 (s,
27H), 0.19 (s, 27H) ppm. 13C NMR (C6D6) d = 134.6,
125.0, 107.4, 93.4, À1.5, À8.0 ppm. 29Si NMR (C6D6)
d = À15.3, À64.2 ppm.
5. Supplementary data
[12] (a) E. Hengge, A. Baumegger, M. Eibl, E. Hohenester, C. Kratky,
Angew. Chem. 102 (1990) 722–724;
Crystallographic data (excluding structure factors) for
the structures of compounds 5 and 6 reported in this paper
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-
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(b) P.B. Hitchcock, M.F. Lappert, M. Layh, Angew. Chem. 111
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Angew. Chem., Int. Ed. Engl. 38 (1999) 501–504.