2,2′-Silaspirobiindan and several related compounds containing group 14 elements are synthesised and characterised. The absorption and fluorescence spectra of the spiro compounds do not show any π–π interaction between two aryl groups, although di-, tri-, tetra-benzyl substituted silanes show the typical intramolecular excimer fluorescence.
References
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Synthesis of 2,2′-stannaspirobiindan (2d) was reported by Lappert, et al. LappertM. F., LeungW.-P., RatsonC. L., SkeltonB. W., and WhiteA. H., J. Chem. Soc., Dalton Trans., 1992, 775.
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29Si NMR spectra of 2b and 2,2-dimethyl-2-silaindan in CDCl3 showed singlets at 33.3 and 17.1ppm.
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Crystal data for 2c: C16H16Ge, monoclinic, a = 14.177(3), b = 11.173(2), c = 8.247(2) Å, β = 103.84(2)°, V = 1268.3(5) Å3, space group C2/c(#15), Dc = 1.471 g/cm3, Z = 4, μ(Mo-Kα) = 23.88 cm−1. 1468 (I > −10.0σ (I)) reflections were used in the structure determination with 78 parameters. Final refinements converged to R (Rw) = 0.059 (0.067). S = 1.52. Dihedral angle between least squares planes (benzene rings); 87.05(8)°. Details will be published elsewhere.
17.
Irradiation of 2b in benzene or acetonitrile did not give any product and 2b was recovered quantitatively. On the other hand, irradiation of an acetonitrile solution containing 2b and p-dicyanobenzene in the presence of phenanthrene as a redox photosensitizer gave o-xylene and 1,2-bis(o-methylphenyl)ethane as C-Si bond cleavage products and (p-cyanophenyl)(o-methylphenyl)methane as a substitution product in 15, 9, and 13% yields, respectively. These results clearly showed that 2b served as an electron donor in the photoinduced electron transfer reactions. Cf. MizunoK., IkedaM., and OtsujiY., Tetrahedron Lett., 1985, 26, 461; K. Nakanishi, K. Mizuno, and Y. Otsuji, Bull. Chem. Soc. Jpn., 1993, 66, 2371.
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