Theoretical and Experimental Chemistry

, Volume 22, Issue 1, pp 62–67 | Cite as

Quantum chemical analysis of pentacoordination of the silicon atom

  • Yu. L. Frolov
  • S. G. Shevchenko
  • M. G. Voronkov
Brief Communications
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Abstract

In the MNDO approximation with full or partial optimization of geometry, we have calculated the energy characteristics and charge redistribution in the model systems Xax(H3)eqSi...Y with variation in the length of the coordination bond Si ← Y and rehybridization of the AOs of the valence shell of the silicon atom. We have considered the formation of the complex anions X=H, F, Cl; Y=H (I) and the complex X=F, Y=O=CH-OH (II). Upon formation of the intramolecular coordination bond Si ← Y, transfer of electron density occurs to the axial and equatorial atoms surrounding the silicon. We have calculated the complexation energy (kJ/ mole): −253.9 (X=H, Y=H), −273.2 (X=F, Y=H), −298.7 (X=Cl, Y=H) and 72.4 for X=F, Y=O=CH-OH.

Keywords

Silicon Chemical Analysis Quantum Chemical Silicon Atom Energy Characteristic 

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Literature cited

  1. 1.
    M. G. Voronkov, I. B. Mazheika, and G. I. Zelchan, “Atranes. 2. Dipole moments and structure of silatranes,” Khim. Geterotsikl. Soedin., No. 1, 58–63 (1965).Google Scholar
  2. 2.
    M. G. Voronkov, V. M. Dyakov, and S. V. Kirpichenko, “Silatranes,” J. Organometal. Chem., 233, No. 1, 1–147 (1982).Google Scholar
  3. 3.
    S. G. Shevchenko, V. P. Elin, G. N., Dolenko, et al., “Study of the structure of silatrane molecules by x-ray fluorescence spectroscopy,” Dokl. Akad. Nauk SSSR, 264, No. 2, 373–376 (1982).Google Scholar
  4. 4.
    P. Baybutt, “The molecular orbital description of SN2 reactions at silicon centers,” Mol. Phys., 29, No. 2, 389–403 (1975).Google Scholar
  5. 5.
    N. M. Vitkovskaya, V. B. Mantsivoda, T. E. Moskovskaya, and M. G. Voronkov, “Quantum-chemical investigation of the silicon and carbon coordination bond in their isostructural compounds,” Int. J. Quant. Chem., 17, No. 2, 299–305 (1980).Google Scholar
  6. 6.
    C. J. Marsden, “Structure and energetics of SiF3NH3 ab initio molecular orbital calculations,” Inorg. Chem., 22, No. 22, 3177–3178 (1983).Google Scholar
  7. 7.
    M. J. S. Dewar and W. Thiel, “Ground states of molecules. 38. The MNDO method approximations and parameters,” J. Am. Chem. Soc., 99, No. 15, 4899–4907 (1977).Google Scholar
  8. 8.
    M. J. S. Dewar and D. H. Lo, “Ground states of σ-bonded molecules. 17. Fluorine compounds,” J. Am. Chem. Soc., 94, No. 15, 5296–5303 (1972).Google Scholar
  9. 9.
    H. Umeyama and K. Morokuma, “Molecular orbital studies of electron donor-acceptor complexes. 3. Energy and charge decomposition analyses for several strong complexes,” J. Am. Chem. Soc., 98, No. 23, 7208–7220 (1976).Google Scholar
  10. 10.
    R. I. P. Corriu and M. Henner, “The siliconium ion question,” J. Organometal. Chem., 74, No. 1, 1–28 (1974).Google Scholar
  11. 11.
    M. G. Voronkov, G. Zelcans, I. Mazeika, et al., “Silatranes: intracomplex heterocyclic compounds of pentacoordinated silicon,” Pure Appl. Chem., 13, No. 1, 35–39 (1966).Google Scholar
  12. 12.
    M. P. Demidov, G. G. Aleksandrov, Yu. T. Struchkov, et al., “Crystal and molecular structure of 3,7,10-trimethylsilatrane,” Koord. Khim., 7, No. 8, 1262–1267 (1981).Google Scholar
  13. 13.
    V. F. Sidorkin, V. A. Pestunovich, and M. G. Voronkov, “Physical chemistry of silatranes,” Usp. Khim., 49, No. 5, 789–813 (1980).Google Scholar
  14. 14.
    Y. L. Frolov, M. G. Voronkov, G. A. Gavrilova, et al., “Intramolecular coordination in methyl(aroyloxymethyl)fluorosilanes,” J. Organometal. Chem., 244, No. 2, 107–114 (1983).Google Scholar
  15. 15.
    M. G. Boronkov, E. I. Brodskaya, P. Reich, et al., “The influence of intermolecular interactions on the Si-H bond vibration in silatrane and its C-substituents,” J. Organometal. Chem., 164, No. 1, 35–40 (1979).Google Scholar
  16. 16.
    V. F. Sidorkin, V. A. Pestunovich, and M. G. Voronkov, “Structure of silatranes within the framework of hypervalent bond theory,” Dokl. Akad. Nauk SSSR, 235, No. 6, 1363–1366 (1977).Google Scholar
  17. 17.
    É. A. Zel'bst, V. E. Shklover, Yu. T. Struchkov, et al., “Crystal structure of organosilicon compounds. 25. (4-halobenzoyloxymethyl)trifluorosilanes,” Zh. Strukt. Khim., 22, No. 3, 82–88 (1981).Google Scholar
  18. 18.
    N. M. Vitkovskaya, V. B. Mantsivoda, O. Yu. Dolgunicheva, and M. G. Voronkov, “Comparative nonempirical calculations of the electronic structures of compounds of pentacoordinated and tetracoordinated silicon,” Dokl. Akad. Nauk SSSR, 238, No. 5, 1098–1101 (1978).Google Scholar

Copyright information

© Plenum Publishing Corporation 1986

Authors and Affiliations

  • Yu. L. Frolov
    • 1
  • S. G. Shevchenko
    • 1
  • M. G. Voronkov
    • 1
  1. 1.Irkutsk Institute of Organic Chemistry, Siberian BranchAcademy of Sciences of the USSRUSSR

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