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When a 2.2 equiv molar amount of lithium naphthalenide was added to a THF solution of 4 at -78 °C, the mixture of 4 and bromosilane 6 was obtained. The use of a 4.2 equiv molar amount of lithium naphthalenide resulted in the formation of compounds 5 and 6 We postulated the mechanism where the silylene was generated by the reduction of the dibromosilane moiety inserted intramolecularly into the C-Br bond, and then hydrosilane 5 was formed by the further reduction of the Si-Br bond of 6 by lithium naphthalenide.
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When a 2.2 equiv molar amount of lithium naphthalenide was added to a THF solution of 4 at -78 °C, the mixture of 4 and bromosilane 6 was obtained. The use of a 4.2 equiv molar amount of lithium naphthalenide resulted in the formation of compounds 5 and 6 We postulated the mechanism where the silylene was generated by the reduction of the dibromosilane moiety inserted intramolecularly into the C-Br bond, and then hydrosilane 5 was formed by the further reduction of the Si-Br bond of 6 by lithium naphthalenide.
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33645680741
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The photophysical and photochemical processes of 9-silaphenanthrene derivatives at 77 K have been reported, and the fluorescence spectrum of 9-Tbt-9-silaphenanthrene is shown there. The lifetimes of the fluorescence of Tbt-9-silaphenanthrene were 6.9 ns (94%) and 2.4 ns (6%). Hiratsuka, H.; Horiuchi, H.; Furukawa, Y.; Watanabe, H.; Ishihara, A.; Okutsu, T.; Tobita, S.; Yoshinaga, T.; Shinohara, A.; Tokitoh, N.; Oba, M.; Nishiyama K. J. Phys. Chem. A 2006, 110, 3868.
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The photophysical and photochemical processes of 9-silaphenanthrene derivatives at 77 K have been reported, and the fluorescence spectrum of 9-Tbt-9-silaphenanthrene is shown there. The lifetimes of the fluorescence of Tbt-9-silaphenanthrene were 6.9 ns (94%) and 2.4 ns (6%). Hiratsuka, H.; Horiuchi, H.; Furukawa, Y.; Watanabe, H.; Ishihara, A.; Okutsu, T.; Tobita, S.; Yoshinaga, T.; Shinohara, A.; Tokitoh, N.; Oba, M.; Nishiyama K. J. Phys. Chem. A 2006, 110, 3868.
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Calculated at the B3LYP/6-31G(d) level. Results of the theoretical calculations for lb are shown in the Supporting Information.
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Calculated at the B3LYP/6-31G(d) level. Results of the theoretical calculations for lb are shown in the Supporting Information.
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31
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1842555193
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Although the degree of T-shaped CH-π interaction should be discussed on the basis of the distance between the center of the aromatic ring and the aromatic plane, it is somewhat difficult to define the center of the 9-silaphenanthrene ring due to the slight deformation of the skeleton. It was reported that the T-shaped CH-π interaction in a benzene dimer should be highly effective when the distance between the center of the aromatic ring and the aromatic plane is ca. 5.0 Å; that is, that between the C atom at the edge and the aromatic plane is ca. 3.6 Å;. The C-C distance (ca 3.7 Å) due to the CH-π interaction observed for la should be similar to those observed for phenanthrene. See: (a) Mason, R. Mol. Phys. 1961, 4, 413
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Although the degree of T-shaped CH-π interaction should be discussed on the basis of the distance between the center of the aromatic ring and the aromatic plane, it is somewhat difficult to define the center of the 9-silaphenanthrene ring due to the slight deformation of the skeleton. It was reported that the T-shaped CH-π interaction in a benzene dimer should be highly effective when the distance between the center of the aromatic ring and the aromatic plane is ca. 5.0 Å; that is, that between the C atom at the edge and the aromatic plane is ca. 3.6 Å;. The C-C distance (ca 3.7 Å) due to the CH-π interaction observed for la should be similar to those observed for phenanthrene. See: (a) Mason, R. Mol. Phys. 1961, 4, 413.
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