Chemical bonding in oxofluorides of hypercoordinate sulfur

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Terence P. Cunningham, David L. Cooper, Joseph Gerratt, Peter B. Karadakov and Mario Raimondi


Abstract

Modern valence bond theory, in its spin-coupled form, is used to investigate the bonding in sulfuryl fluoride, SO2F2, and in the thionyl fluorides, SOF2 and SOF4. Analogous calculations are also carried out for SO2, SO3 and SF4, to enable various comparisons to be made. We find that the sulfur atoms in these systems utilize all six valence electrons in two-centre two-electron polar covalent bonds and in angularly split lone-pair-like orbitals. Although based on just a single orbital configuration, the spin-coupled wavefunction provides a significant energy improvement over the corresponding restricted Hartree–Fock calculation. The spin-coupled description of the S[double bond, length as m-dash]O and S–F bonding, and of the non-bonding electrons on sulfur, turns out to be highly transferable. We find that the S–O π bonds are significantly more polar than the S–O σ bonds. We find no evidence to support notions of pπ–dπ back-donation from oxygen to sulfur. We examine also the ‘equivalent’ or ‘bent-bond’ model of the SO units in the thionyl fluorides.


References

  1. H. Wallmeier and W. Kutzelnigg, J. Am. Chem. Soc., 1979, 101, 2804 CrossRef CAS; W. Kutzelnigg, Angew. Chem., Int. Ed. Engl., 1984, 23, 272 CrossRef.
  2. E. Magnusson and H. F. Schaefer, J. Chem. Phys., 1985, 83, 5721 CrossRef CAS.
  3. A. E. Reed and F. Weinhold, J. Am. Chem. Soc., 1986, 108, 3586 CrossRef CAS.
  4. C. H. Patterson and R. P. Messmer, J. Am. Chem. Soc., 1989, 111, 8059 CrossRef CAS; 1990, 112, 4138.
  5. A. E. Reed and P. v. R. Schleyer, J. Am. Chem. Soc., 1990, 112, 1434 CrossRef CAS.
  6. E. Magnusson, J. Am. Chem. Soc., 1990, 112, 7940 CrossRef CAS; 1993, 115, 1051.
  7. R. P. Messmer, J. Am. Chem. Soc., 1991, 113, 433 CrossRef CAS.
  8. D. L. Cooper, T. P. Cunningham, J. Gerratt, P. B. Karadakov and M. Raimondi, J. Am. Chem. Soc., 1994, 116, 4414 CrossRef CAS.
  9. T. P. Cunningham, D. L. Cooper, J. Gerratt, P. B. Karadakov and M. Raimondi, Int. J. Quant. Chem., 1996, 60, 393 CrossRef CAS.
  10. M. Häser, J. Am. Chem. Soc., 1996, 118, 7311 CrossRef.
  11. J. Gerratt and W. N. Lipscomb, Proc. Natl. Acad. Sci. USA, 1968, 59, 332 CAS.
  12. For recent reviews see: D. L. Cooper, J. Gerratt and M. Raimondi, Adv. Chem. Phys., 1987, 69, 319 Search PubMed; D. L. Cooper, J. Gerratt and M. Raimondi, Chem. Rev., 1991, 91, 929 CAS.
  13. R. C. Ladner and W. A. Goddard III, J. Chem. Phys., 1969, 51, 1073 CrossRef CAS.
  14. D. Kivelson, J. Chem. Phys., 1953, 22, 904.
  15. Y. Morino, Y. Kikuchi, S. Saito and E. Hirota, J. Mol. Spectrosc., 1964, 13, 95 CrossRef CAS.
  16. A. H. Clark and B. Beagley, Trans. Faraday Soc., 1971, 67, 2216 RSC.
  17. R. C. Ferguson, J. Am. Chem. Soc., 1954, 76, 850 CrossRef CAS.
  18. I. Hargittai and F. C. Mijlhoff, J. Mol. Struct., 1973, 16, 69 CrossRef CAS.
  19. D. R. Lide, D. E. Mann and R. M. Fristrom, J. Chem. Phys., 1957, 26, 734 CrossRef CAS.
  20. K. Kimura and S. H. Bauer, J. Chem. Phys., 1963, 39, 3172 CrossRef CAS.
  21. S. H. Tolles and S. H. Gwinn, J. Chem. Phys., 1962, 36, 1119 CrossRef.
  22. MOLPRO is a package of ab initio programs written by H.-J. Werner and P. J. Knowles, with contributions from J. Almlöf, R. D. Amos, A. Berning, M. J. O. Deegan, F. Eckert, S. T. Elbert, C. Hampel, R. Lindh, W. Meyer, A. Nicklaβ, K. Peterson, R. Pitzer, A. J. Stone, P. R. Taylor, M. E. Mura, P. Pulay, M. Schütz, H. Stoll, T. Thorsteinsson and D. L. Cooper.
  23. T. H. Dunning, Jr., J. Chem. Phys., 1971, 55, 716 CrossRef.
  24. A. D. McLean and G. S. Chandler, J. Chem. Phys., 1980, 72, 5639 CrossRef CAS.
  25. J. Pipek and P. G. Mezey, J. Chem. Phys., 1989, 90, 4916 CrossRef CAS; D. L. Cooper, J. Gerratt and M. Raimondi, J. Mol. Struct. (THEOCHEM), 1991, 229, 155 CrossRef.
  26. D. L. Cooper, J. Gerratt, M. Raimondi, M. Sironi and T. Thorsteinsson, Theor. Chim. Acta, 1993, 85, 261 CAS.
  27. See e.g., R. Pauncz, Spin Eigenfunctions, Plenum, New York, 1979 Search PubMed; P. B. Karadakov, J. Gerratt, D. L. Cooper and M. Raimondi, Theor. Chim. Acta, 1995, 90, 51 Search PubMed.
  28. R. Serber, Phys. Rev., 1934, 45, 461 CrossRef; R. Serber, J. Chem. Phys., 1934, 2, 697 CrossRef CAS.
  29. T. P. Cunningham, Ph. D. Thesis, University of Liverpool, 1995.
  30. P. B. Karadakov, J. Gerratt, D. L. Cooper and M. Raimondi, J. Am. Chem. Soc., 1993, 115, 6863 CrossRef CAS.
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