Molecular modelling studies on the reactions of fluoroalkenes with sulfur trioxide

Abstract

The structures, molecular energies and electronic properties of a series of substituted fluoroalkenes and the corresponding alkane sultones, derived from the addition of sulfur trioxide to the double bond, have been explored using a combination of molecular modelling and theoretical calculations. Both the calculated charge distributions at carbon and the calculated enthalpies of the addition process show a good correlation with the observed selectivity of electrophilic attack by the sulfur atom of sulfur trioxide, especially for unsymmetrical alkenes where there are two possible sites of addition. Mechanistically, the reactions of ethene and tetrafluoroethene with sulfur trioxide proceed via formation of stable π-complexes to give a transition state in the former case which is predicted to have a comparable energy to that found experimentally for the related reaction of octadec-1-ene.

References

1. D. W. Roberts and D. L. Williams, J. Chem. Soc., Perkin Trans. 2, 1985, 81, 389.
2. I. L. Knunyants and G. A. Sokolski, Angew. Chem., Int. Ed. Engl., 1972, 11, 583.
3. D. C. England, M. A. Dietrich and R. V. Lindsey Jr., J. Am. Chem. Soc., 1960, 82, 6181.
4. D. W. Roberts and D. L. Williams, Tetrahedron, 1987, 43, 1027.
5. E. E. Gilbert, Chem Rev., 1966, 62, 549.
6. M. A. Dmitriev, G. A. Sokolski and I. L. Knunyants, Khim. Nauka Prom., 1958, 3, 826; Chem. Abstr., 1959, 53, 11211.
7. M. J. S. Dewar and W. Thiel, J. Am. Chem. Soc., 1977, 99, 4899.
8. M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902.
9. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209.
10. M. J. S. Dewar and Y.-C. Yuan, Inorg. Chem., 1990, 29, 3881.
11. (a) J. O. Morley and M. H. Charlton, Int. J. Quantum Chem., 1995, 55, 361; (b) J. O. Morley, Int. J. Quantum Chem., 1998, 66, 141.
12. MOPAC 93, J. J. P. Stewart, Fujitsu Limited, Tokyo, Japan, 1993, obtained from QCPE, Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
13. See for example: W. J. Hehre, L. Radom, P. v. R. SchleyerJ. A. Pople, Ab Initio Molecular Orbital Theory, John Wiley and Sons, New York, 1986.
14. M. F. Guest and P. Sherwood, GAMESS, an ab initio program, The Daresbury Laboratory, Warrington, UK.
15. See C. Wohlfarth, CRC Handbook of Chemistry and Physics, ed. D. R. Lide and H. P. R. Frederiske, CRC Press, Boca Raton, Florida, 1998, 78th edn., pp. 6–139.
16. (a) C. Moller and M. S. Plesset, Phys. Rev., 1934, 46, 618; (b) J. E. Rice, R. D. Amos, N. C. Handy, T. J. Lee and H. F. Schaefer, J. Chem. Phys., 1986, 85, 963; (c) J. D. Watts and M. Dupuis, J. Comput. Chem., 1988, 9, 158.
17. S. Miertus, E. Scrocca and J. Tomasi, Chem. Phys., 1981, 55, 117.
18. SYBYL, Ver. 6.2, Tripos Inc., 1699 S. Hanley Road, St. Louis, Missouri, 63144-2913, USA.
19. S. Nagase and K. Morokuma, J. Am. Chem. Soc., 1978, 100, 1666.
20. A. Bottoni, J. Chem. Soc., Perkin Trans. 2, 1996, 2041.
21. D. Suarez, J. A. Sordo and T. L. Sordo, J. Phys. Chem., 1996, 100, 13462.
22. J. O. Morley and D. W. Roberts, J. Org. Chem., 1997, 62, 7358.
23. Cambridge Structural Database, Cambridge Crystallographic Data Centre, University Chemical Laboratory, Lensfield Road, Cambridge, UK CB2 2EW.
24. R. M. Schonk, B. H. Bakker and H. Cerfontain, Recl. Trav. Chim. Pays-Bas, 1992, 111, 478.
25. K. A. Potekhin, Yu. T. Struchkov, A. S. Koz'min, V. V. Zhdankin, V. D. Sorokin and N. S. Zefirov, Sulf. Lett., 1988, 8, 55.
26. S. Fleck, R. Gockel and A. Weiss, J. Mol. Struct., 1987, 161, 139.
27. C. W. Bock, P. George, G. J. Mains and M. Trachtman, J. Chem. Soc., Perkin Trans. 2, 1979, 814.
28. T. Miyauchi, T. Kikuchi, T. Ogoshi, R. Susuki and H. Kataoka, J. Chem. Eng. Jpn., 1971, 4, 44.