Abstract
Vinyl fluoride reacts with strong bases to afford I-fluorovinyl anion (1a) and a fluoride-acetylene cluster (1b). The former ion can be prepared independently, and cleanly, by the fluorodesilylation of 1-(trimethylsilyl) fluoroethylene. Reactions of 1a are reported, and its proton affinity is assigned (387 ± 3 kcal mol−1). Vinyl fluoride is 22 kcal mol−1 more acidic than ethylene. This unusually large substituent effect is reproduced by ab initio calculations, and can be accounted for by geometric changes which minimize the electron-electron repulsion in 1a. Computations on 2-fluorovinyl anions (1c and 1d) have also been carried out, and both ions are only slightly less stable than 1a. The cis isomer (1c) has a larger barrier for fluoride elimination and is a reasonable target for preparation.
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Taft, R. W. Prog. Phys. Org. Chem. 1987, 16, 1–83. (b) Taft, R. W. Prog. Phys. Org. Chem. 1983, 14, 247-350. (c) Taft, R. W.; Koppel, I. A.; Topsom, R. D.; Anvia, F. J. Am. Chem. Soc. 1990, 112, 2047–2052, and references therein.
Dahlke, G. D.; Kass, S. R. J. Am. Chem. Soc. 1991, 113, 5566–5573.
Dahlke, G. D.: unpublished results.
Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.
Faird, R.; McMahon, T. B. Can. J. Chem. 1980, 58, 2307–2311.
Sullivan, S. A.; Beauchamp, J. L. J. Am. Chem. Soc. 1977, 99, 5017–5022.
Larson, J. W.; McMahon, T. B. J. Am. Chem. Soc. 1985, 107, 766–773. (b) Roy, M.; McMahon, T. B. Can J. Chem. 1985, 63, 708-715. (c) Larson, J. W.; McMahon, T. B. J. Am. Chem. Soc. 1983, 105, 2944–2950.
Kass, S. R.; Guo, H.; Dahlke, G. D. J. Am. Soc. Mass Spectrom. 1990, 1, 366–371.
Caldwell, G.; Bartmess, J. E. Org. Mass Spectrom. 1982, 17, 456–457.
Haszeldine, R. N.; Pool, C. R.; Tipping, A. E. J. Chem. Soc. Dalton Trans. 1975, 2177-2181. (b) Drakesmith, F. G.; Stewart, O. J.; Tarrant, P. J. Org. Chem. 1968, 33, 472–474.
Boeckman, R. K. Jr.: Blum, D. M.; Ganem, B.; Halvey, N. Org. Syn. 1978, 58, 152–157.
Umemoto, T.; Fukami, S.; Tomizawa, G.; Harasawa, K.; Kawada, K.; Tomita, K. J. Am. Chem. Soc. 1990, 112, 8563–8575. (b) Umemoto, T.; Tomita, K.; Kawada, K. Org. Syn. 1990, 69, 129–143.
Frisch, M. J.; Head-Gordon, M.; Trucks, G. W.; Foresman, J. B.; Schlegel, H. B.; Raghavachari, K; Robb, M.; Binkley, J. S.; Gonzalez, C.; Defrees, D. J.; Fox, D. J.; Whiteside, R. A. ; Seeger, R.; Melius, C. F.; Baker, J.; Martin R. L.; Kahn, L. R.; Stewart, J. J. P.; Topiol, S.; Pople, J. A. Gaussian 90 Revision F; Gaussian, Inc., Pittsburgh, PA 1990.
Hariharan, P. C., Pople, J. A. Theor. Chim. Acta 1973, 28, 213–222. (b) Spitznegel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363–371. (c) Clark, T.; Chandrasekhar, J.; Spitznegel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294–301. (d) Møller, C., Plesset, M. S. Phys. Rev. 1934, 46, 618–622. (e) Pople, J. A.; Binkley, J. S.; Seeger, R. Int. J. Quantum Chem. Symp. 1976, 10, 1–19.
Hehre, W. I.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; John Wiley & Sons: New York, 1986.
16. DePuy, C. H. Org. Mass Spectrom. 1985, 20, 556–559.
Chou, P. K.; Kass, S. R. J. Am. Chem. Soc. 1991, 113, 4357–4359. (b) O’Hair, R. A. J.; Gronert, S.; DePuy, C. H.;
Bowie, J. H. J. Am. Chem. Soc. 1989, 111, 3105–3106, and references therein.
Ervin, K. M.; Gronert, S.; Barlow, S. E.; Gilles, M. K.; Harrison, A. G.; Bierbaum, V. M.; DePuy, C. H.; Lineberger, W. c.; Ellison, G. B. J. Am. Chem. Soc. 1990, 112, 5750–5759.
Wiberg, K B. J. Org. Chem. 1991, 56, 544–550.
Herzberg, G. Molecular Spectra and Molecular Structure III. Electronic Spectra and Electronic Structure of Polyatomic Molecules, Van Nostrand: New York, 1966. (b) Huisman, P. A. G.; Mijlhoff, F. C; Renes, G. H. J. Mol. Struct. 1979, 51, 191–209. (c) Carlos, J. L. Jr.: Larl, R. R. [r.: Bauer, S. H. J. Chem. Soc. Faraday Trans. II 1974, 70, 177–187.
Graul, S. T.; Squires, R. R. J. Am. Chem. Soc. 1990, 112, 2517–2529.
Chandrakekhar, J.; Andrade, J. G.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 5612–5614.
Bach, R. D.; Evans, J. C. J. Am. Chem. Soc. 1986, 108, 1374–1379. (b) Caramella, P.; Houk, K. N. Tetrahedron Lett. 1981, 22, 819–822.
Ritchie, J. P.; Bachrach, S. M. J. Am. Chem. Soc. 1990, 112, 6514–6517.
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Rabasco, J.J., Kass, S.R. Reactions of strong bases with vinyl fluoride formation and characterization of 1-fluorovinyl anion and the fluoride-acetylene hydrogen-bonded complex. J Am Soc Mass Spectrom 3, 91–98 (1992). https://doi.org/10.1016/1044-0305(92)87041-V
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DOI: https://doi.org/10.1016/1044-0305(92)87041-V