Gas-phase reactivity of rare earth cations with phenol: Competitive activation of C-O, O-H, and C-H bonds

  • José M. Carretas
  • António Pires de Matos
  • Joaquim Marçalo
  • Marc Pissavini
  • Michele Decouzon
  • Serge Géribaldi
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Abstract

The gas-phase reactions of Sc+, Y+, and Ln+ (Ln=La-Lu, except Pm) ions with phenol were studied by Fourier transform ion cyclotron resonance mass spectrometry. All the ions except Yb+ were observed to react with the organic substrate, activating O-H, C-O, and/or C-H bonds, with formation of MO+, MOH+, and/or MOC6H 4 + ions as primary products. The product distributions and the reaction efficiencies obtained showed the existence of important differences in the relative reactivity of the rare earth metal cations, which are discussed in terms of factors like the electron configurations of the metal ions, their oxophilicity, and the second ionization energies of the metals. The primary product ions participated in subsequent reactions, yielding species such as M(OH)(OC6H5)+, which lead mainly to M(OC6H5)2(HOC6H5) n + ions, where n=0–2. Formation of M(OC6H5)(HOC6H5) n + species was also observed in the case of the metals that have high stabilities of the formal oxidation state 2+, Sm and Eu.

Keywords

Rare Earth Metal High Excitation Energy Bond Dissociation Enthalpy Rare Earth Cation Formal Oxidation State 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References

  1. 1.
    Eller, K.; Schwarz, H. Chem. Rev. 1991, 91, 1121.CrossRefGoogle Scholar
  2. 2.
    Beauchamp, J. L.; van Koppen, P. A. M. In Energetics of Organometallic Species; Martinho Simões, J. A. Ed.; NATO ASI Series, Kluwer: Dordrecht, 1992; p 287.Google Scholar
  3. 3.
    Armentrout, P. B.; Clemmer, D. E. In Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; NATO ASI Series, Kluwer: Dordrecht, 1992; p 321.Google Scholar
  4. 4.
    Weisshaar, J. C. Acc. Chem. Res. 1993, 26, 213.CrossRefGoogle Scholar
  5. 5.
    Bowers, M. T. Acc. Chem. Res. 1994, 27, 324.CrossRefGoogle Scholar
  6. 6.
    Freiser, B. S. Acc. Chem. Res. 1994, 27, 353.CrossRefGoogle Scholar
  7. 7.
    Huang, Y.; Wise, M. B.; Jacobson, D. B.; Freiser, B. S. Organometallics 1987, 6, 346.CrossRefGoogle Scholar
  8. 8.
    Huang, Y.; Hill, Y. D.; Sodupe; M.; Bauschlicher, C. W., Jr; Freiser, B. S. Inorg. Chem. 1991, 30, 3822.CrossRefGoogle Scholar
  9. 9.
    Schilling, J. B.; Beauchamp, J. L. J. Am. Chem. Soc. 1988, 110, 15.CrossRefGoogle Scholar
  10. 10.
    Sunderlin, L. S.; Armentrout, P. B. J. Am. Chem. Soc. 1989, 111, 3845.CrossRefGoogle Scholar
  11. 11.
    Azzaro, M.; Breton, S.; Decouzon, M.; Geribaldi, S. Int. J. Mass Spectrom. Ion Processes 1993, 128, 1.CrossRefGoogle Scholar
  12. 12.
    Geribaldi, S.; Breton, S.; Decouzon, M.; Azzaro, M. J. Am. Soc. Mass Spectrom. 1996, 7, 1151.CrossRefGoogle Scholar
  13. 13.
    Yin, W. W.; Marshall, A. G.; Marçalo, J.; Pires de Matos, A. J. Am. Chem. Soc. 1994, 116, 8666.CrossRefGoogle Scholar
  14. 14.
    Leal, J. P.; Marçalo, J.; Pires de Matos, A.; Marshall, A. G.; Yin, W. W.; Spirlet, J.-C. Proceedings of the 2nd European FTMS Workshop; Antwerp, 1993; Van Vaeck, L., Ed.; University of Antwerp (UIA), 1994; p 312.Google Scholar
  15. 15.
    Marçalo, J.; Pires de Matos, A.; Evans, W. J. Organometallics 1996, 15, 345.CrossRefGoogle Scholar
  16. 16.
    Marçalo, J.; Pires de Matos, A.; Evans, W. J. Organometallics 1997, 16, 3845.CrossRefGoogle Scholar
  17. 17.
    Heinemann, C.; Schröder, D.; Schwarz, H. Chem. Ber. 1994, 127, 1807.CrossRefGoogle Scholar
  18. 18.
    Heinemann, C.; Goldberg, N.; Tornieporth-Oetting, I. C.; Klapötke, T. M.; Schwarz, H. Angew. Chem. Int. Ed. Engl. 1995, 34, 213.CrossRefGoogle Scholar
  19. 19.
    Cornehl, H. H.; Heinemann, C.; Schröder, D.; Schwarz, H. Organometallics 1995, 14, 992.CrossRefGoogle Scholar
  20. 20.
    Heinemann, C.; Cornehl, H. H.; Schröder, D.; Dolg, M.; Schwarz, H. Inorg. Chem. 1996, 35, 2463.CrossRefGoogle Scholar
  21. 21.
    Cornehl, H. H.; Hornung, G.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 9960.CrossRefGoogle Scholar
  22. 22.
    Cornehl, H. H.; Wesendrup, R.; Diefenbach, M.; Schwarz, H. Chem. Eur. J. 1997, 3, 1083.CrossRefGoogle Scholar
  23. 23.
    Gibson, J. K. J. Fluorine Chem. 1996, 78, 65.CrossRefGoogle Scholar
  24. 24.
    Gibson, J. K. J. Phys. Chem. 1996, 100, 15688.CrossRefGoogle Scholar
  25. 25.
    Hubert-Pfalzgraf, L. New J. Chem. 1995, 19, 727.Google Scholar
  26. 26.
    Tsuneo, I. Lanthanides in Organic Synthesis; Academic: London, 1994.Google Scholar
  27. 27.
    Carretas, J. M.; Marçalo, J.; Pires de Matos, A.; Marshall, A. G. 14th International Mass Spectrometry Conference, Tampere, Finland, 1997; abstract MoPo008.Google Scholar
  28. 28.
    Marshall, A. G.; Verdun, F. R. Fourier Transforms in NMR, Optical, and Mass Spectrometry—A User’s Handbook; Elsevier: Amsterdam, 1990.Google Scholar
  29. 29.
    Marshall, A. G.; Grosshans, P. B. Anal. Chem. 1991, 63, 215AGoogle Scholar
  30. 30.
    Freiser, J. M., In Techniques for the Study of Ion Molecule Reactions; Farrar, J. M.; Saunders, W. H., Jr, Eds.; Wiley: New York, 1988; p 61.Google Scholar
  31. 31.
    Bjarnason, A.; Taylor, J. W. Organometallics 1990, 9, 1493.CrossRefGoogle Scholar
  32. 32.
    Su, T.; Bowers, M. T. In Gas Phase Ion Chemistry.; Bowers, M. T., Ed.; Academic: New York, 1979; Chap 3.Google Scholar
  33. 33.
    CRC Handbook of Chemistry and Physics, 75th ed.; Lide, D. R., Ed.; CRC: Boca Raton, 1994.Google Scholar
  34. 34.
    Miller, K. J. J. Am. Chem. Soc. 1990, 112, 8533.CrossRefGoogle Scholar
  35. 35.
    Martin, W. C.; Zalubas, R.; Hagan, L. Atomic Energy Levels The Rare-Earth Elements; NSRDS-NBS 60; National Bureau of Standards (NIST): Washington, DC, 1978.Google Scholar
  36. 36.
    Goldschmidt, Z. B. In Handbook on the Physics and Chemistry of Rare Earths, Vol. 1; Gschneidner, K. A.; Eyring, L., Ed.; North Holland: Amsterdam, 1978; Chap 1.Google Scholar
  37. 37.
    Tolbert, M. A.; Beauchamp, J. L. J. Am. Chem. Soc. 1984, 106, 8117.CrossRefGoogle Scholar
  38. 38.
    Chandrasekharaiah, M. S.; Gingerich, K. A. In Handbook on the Physics and Chemistry of Rare Earths, Vol. 12; Gschneidner, K. A.; Eyring, L., Ed.; North Holland: Amsterdam, 1989; p 409.Google Scholar
  39. 39.
    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.Google Scholar
  40. 40.
    Schröder, D.; Schwarz, H. Angew. Chem. Int. Ed. Engl. 1995, 34, 1973.CrossRefGoogle Scholar
  41. 41.
    Bjarnason, A.; Ridge, D. P. J. Phys. Chem. 1996, 100, 15118.CrossRefGoogle Scholar
  42. 42.
    Clemmer, D. E.; Aristov, N.; Armentrout, P. B. J. Phys. Chem. 1993, 97, 544.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 1998

Authors and Affiliations

  • José M. Carretas
    • 1
  • António Pires de Matos
    • 1
  • Joaquim Marçalo
    • 1
  • Marc Pissavini
    • 2
  • Michele Decouzon
    • 2
  • Serge Géribaldi
    • 2
  1. 1.Departamento de QuímicaInstituto Tecnológico e NuclearSacavém CodexPortugal
  2. 2.GRECFO-Chimie-Physique OrganiqueUniversité de Nice-Sophia AntipolisNiceFrance

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