Abstract
The geometry and electronic structure of 1,4-di(silaethen-1-yl)benzene (2), itsmeta- andbrtho-isomers (3 and4, respectively), and its carbon analog, 1,4-divinylbenzene (5), were studied by the semiempirical MNDO-PM3 method. Unlike5, two pairs of the frontier MOs in isomers2–4 are mainly π-orbitals of Si=C bonds, while the structure of the lowest occupied π-MO indicates delocalization of π-electrons of the entire system. The main characteristic features of the double Si=C bonds (the high polarity and narrow HOMO-LUMO energy gap, which favors the [2+2]-cycloaddition reaction) remain in arylsilenes2–4. The interaction between π-electrons of benzene fragment and the double Si=C bonds results in violation of the benzene ring symmetry, which is most pronounced in structure5. Weakening of the C−H bonds in theortho-positions of the aromatic nucleus in the compounds under study is observed.
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References
M. C. Flowers and L. E. Gusel'nikov,J. Chem. Soc. B, 1968, 419.
V. V. Volkova, L. E. Gusel'nikov, E. A. Volnina, and E. N. Buravtseva,Organometallics, 1994,13, 4661.
L. E. Gusel'nikov, V. V. Volkova, and B. D. Lavrukhin,J. Organomet. Chem., 1995,492, C4.
J. Stewart,J. Computat. Chem., 1989,10, 221.
G. Klopman, inChemical Reactivity and Reaction Path, Wiley, New York, 1974.
H. S. Gutowsky, Jane Chen, P. J. Hajduk, J. D. Keen, C. Chuang, and T. Emilsson,J. Am. Chem. Soc., 1991,113, 4747.
K. Wiberg,Tetrahedron, 1968,24, 1083.
M. Dewar, E. Zoebish, E. Healy, and J. Stewart,J. Am. Chem. Soc., 1985,107, 3902.
Y. Apeloig, inThe Chemistry of Organic Silicon Compounds, Eds. S. Patai and Z. Rappoport, Wiley, New York, 1989, 57.
G. Raabe and J. Michi,Chem. Rev., 1985,85, 419.
R. B. Woodward and R. Hoffmann,Angew. Chem., Int. Ed. Engl., 1969,8, 781.
E. T. Seidl, R. S. Grev, and H. F. Schaefer, III,J. Am. Chem. Soc., 1992,114, 3643.
F. Bernardi, A. Bottoni, M. Olivucci, M. A. Robb, and A. Venturini,J. Am. Chem. Soc., 1993,115, 3322.
F. Bernardi, A. Bottoni, P. Celani, M. Olivucci, M. A. Robb, and A. Venturini,Chem. Phys. Lett., 1992,192, 229.
P. B. Dervan and D. S. Santilli,J. Am. Chem. Soc., 1980,102, 3863.
Y. Apeloig and M. Karni,J. Am. Chem. Soc., 1984,106, 6676.
R. Ahlrich and R. Heinzman,J. Am. Chem. Soc., 1977,99, 7451.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 256–260, February, 1999.
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Timofeeva, L.M., Volkova, V.V. & Gusel'nikov, L.E. Electronic structure, geometry, and reactivity of arylsilenes: a quantum-chemical study. Russ Chem Bull 48, 256–260 (1999). https://doi.org/10.1007/BF02494542
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DOI: https://doi.org/10.1007/BF02494542