Chinese Journal of Organic Chemistry >
Interaction of Silicon-Silicon Bonds and Phenyl Rings: UV Absorption Properties of Unsymmetrically Substituted 1,2 Diphenyltetramethyldisilanes
Received date: 2013-06-21
Revised date: 2013-10-09
Online published: 2013-10-28
Supported by
Project supported by the National Natural Science Foundation of China (No. 20834002), the Natural Science Foundation of Tianjin City, and the Research Found for the Doctoral Program of High Education (No. 20090031110012).
The interaction of silicon-silicon-bonds and phenyl-systems in phenyldisilanes and the resulted characteristic UV absorptions have been one of the fundamental issues of organosilicon chemistry. However, the interaction between two phenyl groups and the central silicon-silicon bond in 1,2-diphenyltetramethyldisilanes and its correlation with the characteristic UV absorptions remain uncompletely solved. In this paper, a series of unsymmetric substituted 1,2-diphenyltetramethyldisilanes, namely C6H5SiMe2SiMe2C6H4-p-COMe (3), p-MeOC6H4SiMe2SiMe2C6H4-p-COMe (4), C6H5SiMe2SiMe2C6H4-p-NMe2 (5) and p-MeOC6H4SiMe2SiMe2C6H4-p-NMe2 (6), have been synthesized and characterized by 1H NMR, 13C NMR, IR and elemental analyses, and their UV absorption properties were studied. It is found that each of the compounds exhibits two characteristic absorption bands at the long wavelength region of the UV spectra, which corresponds to the absorptions produced when individual substituted phenyl groups are linked to silicon-silicon bonds. No obvious bathochromic shifts due to interaction between two substituted phenyl groups through the silicon-silicon bond have been observed. This indicates that the traditional explanation of characteristic UV absorptions of phenyldisilanes in terms of conjugation between silicon-silicon bonds and phenyl groups should be re-examined.
Key words： phenyldisilanes; silicon-silicon bonds; UV absorption; σ-π conjugation; charge transfer
Gu Guangna , Sun Huailin , Zhou Xiuzhong . Interaction of Silicon-Silicon Bonds and Phenyl Rings: UV Absorption Properties of Unsymmetrically Substituted 1,2 Diphenyltetramethyldisilanes[J]. Chinese Journal of Organic Chemistry, 2014 , 34(2) : 349 -354 . DOI: 10.6023/cjoc201306034
[1] For reviews, see:(a) Sakurai, H. J. Organomet. Chem. 1980, 200, 261.
(b) Sakurai, H. Pure Appl. Chem. 1987, 59, 1637.
[2] Sakurai, H.; Kumada, M. Bull. Chem. Soc. Jpn. 1964, 37, 1894.
[3] Gilman, H.; Atwell, W. H.; Schwebke, G. L. J. Organomet. Chem. 1964, 2, 369.
[4] Hague, D. N.; Prince, R. H. Chem. Ind. (London) 1964, 1492.
[5] (a) Sakurai, H.; Yamamori, H.; Kumada, M. Chem. Commun. 1968, 198.
(b) Bock, H.; Alt, H. J. Am. Chem. Soc. 1970, 92, 1569.
[6] (a) Sakurai, H.; Tasaka, S.; Kira, M. J. Am. Chem. Soc. 1972, 94, 9285.
(b) Kira, M.; Miyazawa, T.; Mikami, N.; Sakurai, H. Organometallics 1991, 10, 3793.
[7] Pitt, C. G.; Bock, H. J. Chem. Soc., Chem. Commun. 1972, 28.
[8] Turner, D. W.; Baker, C.; Baker, A. D.; Brundle, C. R. Philos. Trans. R. Soc. London 1970, 268, 7.
[9] Tsuji, H.; Shibano, Y.; Takahashi, T.; Kumada, M.; Tamao, K. Bull. Chem. Soc. Jpn. 2005, 78, 1334.
[10] Traven, V. F.; Eismont, M. Y.; Redchenko, V. V.; Stepanov, B. I. J. Gen. Chem. USSR (Engl. Transl.) 1980, 50, 1615.
[11] Sun, H.-L. M.S. Thesis, Nankai University, Tianjin, 1986 (in Chinese).
(孙怀林, 硕士论文, 南开大学, 天津, 1986.)
[12] (a) Sakurai, H.; Yamamori, H.; Kumada, M. Bull. Chem. Soc. Jpn. 1965, 38, 2024.
(b) Kelling, H. Z. Chem. 1967, 7, 237.
(c) Hiratsuka, H.; Horiuchi, H.; Takanoha, Y.; Matsumoto, H.; Yoshihara, T. Chem. Lett. 2007, 36, 1168.
[13] Sterzycki, R.; Pyridinium, T. Synthesis 1979, 724.
[14] Liu, G. M. M.S. Thesis, Nankai University, Tianjin, 1984 (in Chinese).
(刘钢, 硕士论文, 南开大学, 天津, 1984.)
[15] Katsumi, K.; Saburo, N. Theoret. Ehim. Aeta. (Berl.) 1965, 3, 164.
[16] Van Walree, C. A.; Roest, M. R.; Schuddeboom, W.; Jenneskens, L. W.; Verhoeven, J. W.; Warman, J. M.; Kooijman, H.; Spek, A. L. J. Am. Chem. Soc. 1996, 118, 8395.
[17] Shizuka, H.; Obuchi, H.; Ishikawa, M.; Kumada, M. J. Chem. Soc., Chem. Commun. 1981, 405.
[18] Kira, M.; Miyazawa, T.; Sugiyama, H.; Yamaguchi, M.; Sakurai, H. J. Am. Chem. Soc. 1993, 115, 3116.
[19] Kumada, M.; Ishikawa, M.; Maeda, S. J. Organomet. Chem. 1964, 2, 478.
[20] Jones, K. L.; Pannell, K. H. J. Am. Chem. Soc. 1993, 115, 11336.
[21] Detty, M. R.; Murray, B. J.; Smith, D. L.; Zumbulyadis, N. J. Am. Chem. Soc. 1983, 105, 875.
[22] Miyashita, M.; Yoshikoshi, A.; Grieco, P. A. J. Org. Chem. 1977, 42, 3772.
[23] Gervat, S.; Léonel, E.; Barraud, J. Y.; Ratovelomanana, V. Tetrahedron Lett. 1993, 34, 2115.
[24] (a) Liu, G.; Xu, S.-S; Zhang, B.-S.; Zhou, X.-Z. Chin. J. Org. Chem. 1988, 8, 533 (in Chinese).
(刘钢, 徐善生, 张宝申, 周秀中, 有机化学, 1988, 8, 533.)
(b) Detty, M. R.; Murray, B. J.; Smith, D. L.; Zumbulyadis, N. J. Am. Chem. Soc. 1983, 105, 875.
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