Organometallics
ARTICLE
temperature over 2 h. The orange color of the solution gradually disappeared.
After evaporation of the solvent and remaining methanol, the H NMR
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1
spectrum showed the presence of 5 and 9-methoxy-9-borabicyclo-
[3.3.1]nonane (6). The residue was recrystallized from pentane (0.5 mL)
at room temperature to give 5 as a colorless powder (20 mg, 69% yield): mp
142.3ꢀ144.2 °C; 1H NMR (C6D6, δ) 0.05 (s, 2 H, CH(SiMe3)2), 0.16 (s, 1
H, CH(SiMe3)2), 0.20 (s, 1 H, CH(SiMe3)2), 0.32 (s, 18 H, CH(SiMe3)2),
0.345 (s, 9 H, CH(SiMe3)2), 0.350 (s, 18 H, CH(SiMe3)2), 0.38 (s, 9 H,
CH(SiMe3)2), 0.40 (s, 9 H, CH(SiMe3)2), 0.43 (s, 9 H, CH(SiMe3)2), 1.29
(d, J = 7.2 Hz, 3 H, CH(CH3)2), 1.31 (d, J = 7.2 Hz, 3 H, CH(CH3)2), 1.36
(d, J = 7.2 Hz, 3 H, CH(CH3)2), 1.41 (d, J = 7.2 Hz, 3 H, CH(CH3)2), 1.50
(sept, J = 7.2 Hz, 1 H, CH(CH3)2), 1.58 (sept, J = 7.2 Hz, 1 H, CH(CH3)2),
3.45 (d, J= 5.6 Hz, 1 H, SiH2), 3.50(s, 3H, OMe), 3.66 (dd, J= 5.6, 9.6 Hz, 1
H, SiH2), 5.89 (d, J = 9.6 Hz, 1 H, SiH(OMe)); 13C NMR (C6D6, δ) 5.16
(SiMe3), 5.18 (SiMe3 ꢁ 2), 5.23 (SiMe3), 5.32 (SiMe3), 5.36 (SiMe3), 5.41
(SiMe3), 5.52 (SiMe3), 5.6 (CH(SiMe3)2), 6.1 (CH(SiMe3)2), 7.8 (CH-
(SiMe3)2), 7.9 (CH(SiMe3)2), 17.7 (CH(CH3)2), 17.8 (CH(CH3)2), 21.2
(CH(CH3)2), 21.7 (CH(CH3)2), 21.8 (CH(CH3)2), 21.9 (CH(CH3)2),
57.0 (OMe); 29Si NMR (C6D6, δ) ꢀ96.7 (1JSiꢀH = 167 Hz, SiH2), ꢀ0.4
(SiMe3), ꢀ0.2 (SiMe3), ꢀ0.14 (SiMe3), ꢀ0.09 (SiMe3), 0.1 (SiMe3),
0.2 (SiMe3), 0.4 (SiMe3), 0.6 (SiMe3), 4.3 (SiiPrDsi2), 8.3 (1JSiꢀH = 173 Hz,
SiH(OMe)), 10.6 (SiiPrDsi2); HRMS m/z calcd for C35H95OSi12 [M ꢀ
H]þ 867.4609, found 867.4610.
Reaction of the Boryl-Substituted Disilene 3a with MeOD.
The procedure was the same as for the preparation of 5, except that
methanol-d1 (0.10 mL, 79 mg, 2.5 mmol) was used to provide colorless
5-d2 (15 mg, 53%). 1H NMR analysis showed that 5-d2 is a mixture of
50% 5-2,3-d2 and 50% 5-3,3-d2.
Computational Method. All calculations were carried out using
the Gaussian 03 program.29 Calculations were performed with hybrid
density functional theory at the B3LYP27,28 level, using the basis set
6-31G(d)29 for geometry optimization, 6-311G(3d)28 for the GIAO
method, and 6-31þG(d)29 for the transition state searches.
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Ichinohe, M.; West, R.; Balazs, Y. S.; Schmidt, A.; Karni, M.; Apeloig,
Y. J. Am. Chem. Soc. 2006, 128, 14472.
’ ASSOCIATED CONTENT
(11) Wiberg, N.; Vasisht, S. K.; Fischer, G.; Mayer, P. Z. Anorg. Allg.
Chem. 2004, 630, 1823.
(12) Sasamori, T.; Hironaka, K.; Sugiyama, Y.; Takagi, N.; Nagase,
S.; Hosoi, Y.; Furukawa, Y.; Tokitoh, N. J. Am. Chem. Soc. 2008,
130, 13856.
S
Supporting Information. Tables of crystallographic data
b
including atomic positional and thermal parameters for 3b
(PDF/CIF) and computational details (tables of atomic coordi-
nates for optimized geometries of the model compound 30 and
values of their total energies). This material is available free of
(13) Murata, Y.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2010,
132, 16768.
(14) Kinjo, R.; Ichinohe, M.; Sekiguchi, A.; Takagi, N.; Sumimoto,
M.; Nagase, S. J. Am. Chem. Soc. 2007, 129, 7766.
(15) Kinjo, R.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2007,
’ AUTHOR INFORMATION
Corresponding Author
*Phone:þ81-29-853-4314. Fax: þ81-29-853-4314 E-mail: sekiguch@
129, 26.
(16) Yamaguchi, T.; Ichinohe, M.; Sekiguchi, A. New J. Chem. 2010,
34, 1544.
(17) Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Synth. Met. 2009,
chem.tsukuba.ac.jp.
159, 773.
(18) Takeuchi, K.; Ichinohe, M.; Sekiguchi, A.; Guo, J.-D.; Nagase, S.
Organometallics 2009, 28, 2658.
(19) Takeuchi, K.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc.
2008, 130, 16848.
(20) Takeuchi, K.; Ichinohe, M.; Sekiguchi, A.; Guo, J.-D.; Nagase, S.
J. Phys. Org. Chem. 2010, 23, 390.
(21) Han, J. S.; Sasamori, T.; Mizuhata, Y.; Tokitoh, N. J. Am. Chem.
Soc. 2010, 132, 2546.
’ ACKNOWLEDGMENT
This work was financially supported by Grants-in-Aid for
Scientific Research program (Nos. 19105001, 20038006,
21550033) from the Ministry of Education, Science, Sports,
and Culture of Japan, JSPS Research Fellowship for Young
Scientist (K.T.).
(22) Han, J. S.; Sasamori, T.; Mizuhata, Y.; Tokitoh, N. Dalton Trans.
2010, 39, 9238.
(23) Yamaguchi, T.; Sekiguchi, A.; Driess, M. J. Am. Chem. Soc. 2010,
132, 14061.
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