SpringerLink
Log in

Charge inversion as a structural probe for C6H +5 and C6H +·6 cations

  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

Charge reversal (+CR−) of cations to anions can be used to structurally differentiate isomeric C6H +5 and C6H +·6 hydrocarbon ions by means of tandem mass spectrometry. In view of the manifold of possible isomers, only a few prototype precursors are examined. Thus, charge inversion demonstrates that electron ionization of 2,4-hexadiyne yields an intact molecular ion, whereas the charge inversion spectra of C6H +·6 obtained from benzene, 1,5-hexadiyne, and fulvene are identical within experimental error. Similarly, the +CR− spectrum of the C6H +5 cation generated by dissociative ionization of 2,4-hexadiyne is significantly different from the +CR− spectrum of C6H +5 obtained from iodobenzene, suggesting the formation of a 2,4-hexadiynyl cation from the former precursor. Although charge inversion of cations to anions has a low efficiency and requires large precursor ion fluxes, the particular value of this method is that the spectra may not just differ in fragment ion intensities, but these differences can directly be related to the underlying ion structures.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Germany)

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Rosenstock, H. M.; Dannacher, J.; Liebman, J. F. Radiat. Phys. Chem. 1982, 20, 7.

    CAS  Google Scholar 

  2. Kuck, D. Mass Spectrom. Rev. 1990, 9, 187.

    Article  CAS  Google Scholar 

  3. Baer, T.; Willett, G. D.; Smith, D.; Philips, J. S. J. Chem. Phys. 1979, 70, 4076.

    Article  CAS  Google Scholar 

  4. Neusser, H. J.; Schlag, E. W. Angew. Chem. 1992, 104, 269;

    Article  CAS  Google Scholar 

  5. Angew. Chem., Int. Ed. Engl. 1992, 31, 263.

  6. Miller, D. L.; Gross, M. L. J. Am. Chem. Soc. 1983, 105, 4239.

    Article  CAS  Google Scholar 

  7. Hayward, M. J.; Mabud, Md. A.; Cooks, R. G. J. Am. Chem. Soc. 1988, 110, 1343.

    Article  CAS  Google Scholar 

  8. Vekéy, K. Mass Spectrom. Rev. 1995, 14, 195.

    Article  Google Scholar 

  9. Holmes, J. L.; Mommers, A. A.; Terlouw, J. K.; Hop, C. E. C. A. Int. J. Mass Spectrom. Ion Processes 1986, 68, 249.

    Article  CAS  Google Scholar 

  10. van der Hart, W. J. J. Am. Soc. Mass Spectrom. 1995, 6, 513.

    Article  Google Scholar 

  11. van der Hart, W. J. J. Am. Soc. Mass Spectrom. 1996, 7, 731.

    Google Scholar 

  12. van der Hart, W. J. J. Am. Soc. Mass Spectrom. 1997, 8, 594, 599.

    Article  Google Scholar 

  13. van der Hart, W. J. Int. J. Mass Spectrom. Ion Processes 1998, 176, 23.

    Google Scholar 

  14. Schröder, D.; Oref, I.; Hrušák, J.; Weiske, T.; Nikitin, E. E.; Zummack, W.; Schwarz, H. J. Phys. Chem. A 1999, 103, 4609.

    Article  Google Scholar 

  15. Mason, R. S.; Milton, D. M. P.; Harris, F. J. Chem. Soc., Chem. Commun. 1987, 1453.

  16. Hrušák, J.; Schröder, D.; Weiske, T.; Schwarz, H. J. Am. Chem. Soc. 1993, 115, 2015.

    Article  Google Scholar 

  17. Tkaczyk, M.; Harrison, A. G. Int. J. Mass Spectrom. Ion Processes 1994, 132, 73.

    Article  CAS  Google Scholar 

  18. Mason, R. S.; Parry, A. J.; Milton, D. M. P. J. Chem. Soc., Faraday Trans. 1994, 90, 1373.

    Article  CAS  Google Scholar 

  19. Eyler, J. R.; Campana, J. E. Int. J. Mass Spectrom. Ion Processes 1983/1984, 55, 171.

    Article  Google Scholar 

  20. Speranza, M.; Sefcik, M. D.; Henis, J. M. S.; Gaspar, P. P. J. Am. Chem. Soc. 1977, 99, 5583.

    Article  CAS  Google Scholar 

  21. Wesdemiotis, C.; McLafferty, F. W. Chem. Rev. 1987, 87, 485.

    Article  CAS  Google Scholar 

  22. McMahon, A. W.; Chowdhury, S. K.; Harrison, A. G. Org. Mass Spectrom. 1989, 24, 620.

    Article  CAS  Google Scholar 

  23. Polce, M. J.; Wesdemiotis, C. Rapid Commun. Mass Spectrom. 1996, 10, 235.

    Article  CAS  Google Scholar 

  24. Wesdemiotis, C.; Leyh, B.; Fura, A.; McLafferty, F. W. J. Am. Chem. Soc. 1990, 112, 8655.

    Article  CAS  Google Scholar 

  25. Schröder, D.; Schalley, C. A.; Goldberg, N.; Hrušák, J.; Schwarz, H. Chem. Eur. J. 1996, 2, 1235.

    Article  Google Scholar 

  26. Schalley, C. A.; Fiedler, A.; Friedrichs, H.; Hornung, G.; Wesendrup, R.; Schröder, D.; Schwarz, H. Chem. Eur. J. 1997, 3, 626.

    Article  CAS  Google Scholar 

  27. Feng, R.; Wesdemiotis, C.; Zhang, M.-Y.; Marchetti, M.; McLafferty, F. W. J. Am. Chem. Soc. 1989, 111, 1986.

    Article  CAS  Google Scholar 

  28. Zhang, M. Y.; Wesdemiotis, C.; Marchetti, M.; Danis, P. O.; Ray, J. C.; Carpenter, B. K.; McLafferty, F. W. J. Am. Chem. Soc. 1989, 111, 8341.

    Article  CAS  Google Scholar 

  29. Hayakawa, S.; Endoh, H.; Arakawa, K.; Morishita, N. Int. J. Mass Spectrom. Ion Processes 1997, 171, 209.

    Article  CAS  Google Scholar 

  30. Schroeter, K.; Schröder, D.; Schwarz, H. J. Phys. Chem. A 1999, 103, 4174.

    Article  CAS  Google Scholar 

  31. Drinkwater, D. E.; McLafferty, F. W. Org. Mass Spectrom. 1993, 28, 378.

    Article  CAS  Google Scholar 

  32. Srinivas, R.; Sülzle, D.; Weiske, T.; Schwarz, H. Int. J. Mass Spectrom. Ion Processes 1991, 107, 368.

    Article  Google Scholar 

  33. Srinivas, R.; Sülzle, D.; Koch, W.; DePuy, C. H.; Schwarz, H. J. Am. Chem. Soc. 1991, 113, 5970.

    Article  CAS  Google Scholar 

  34. Schalley, C. A.; Schröder, D.; Schwarz, H. Int. J. Mass Spectrom. Ion Processes 1996, 153, 173.

    Article  Google Scholar 

  35. Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347.

    Article  CAS  Google Scholar 

  36. Raphael, H.; Sondheimer, F. J. Chem. Soc. 1950, 120.

  37. Sturm, E.; Hafner, K. Angew. Chem. 1964, 76, 862;

    Article  CAS  Google Scholar 

  38. Angew. Chem., Int. Ed. Engl. 1964, 3, 749.

  39. Nash, J. J.; Squires, R. R. J. Am. Chem. Soc. 1996, 118, 11872.

    Article  CAS  Google Scholar 

  40. Nicolaides, A.; Smith, D. M.; Jensen, F.; Radom, L. J. Am. Chem. Soc. 1997, 119, 8083.

    Article  CAS  Google Scholar 

  41. Van Orden, A.; Saykally, R. J. Chem. Rev. 1998, 98, 2313.

    Article  Google Scholar 

  42. 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.

  43. Mackay, G. I.; Böhme, D. K. Org. Mass Spectrom. 1980, 15, 593.

    Article  CAS  Google Scholar 

  44. Robinson, M. S.; Polak, M. L.; Bierbaum, V. M.; DePuy, C. H.; Lineberger, W. C. J. Am. Chem. Soc. 1995, 117, 6766.

    Article  CAS  Google Scholar 

  45. Russell, D. H.; Gross, M. L. J. Am. Chem. Soc. 1980, 102, 6279.

    Article  CAS  Google Scholar 

  46. Hrušák, J.; Schröder, D.; Iwata, S. J. Chem. Phys. 1997, 106, 7541.

    Article  Google Scholar 

  47. Harvey, J. N.; Aschi, M.; Schwarz, H.; Koch, W. Theor. Chem. Acc. 1998, 99, 95.

    CAS  Google Scholar 

  48. Wenthold, P. G.; Hu, J.; Squires, R. R. J. Am. Chem. Soc. 1996, 118, 11865.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut für Organische Chemie der Technischen Universität Berlin, D-10623, Berlin, Germany

    Detlef Schröder, Katrin Schroeter, Waltraud Zummack & Helmut Schwarz

Authors
  1. Detlef Schröder
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Katrin Schroeter
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Waltraud Zummack
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Helmut Schwarz
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

In memory of R. R. Squires: a friend and an eminent scientist.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Schröder, D., Schroeter, K., Zummack, W. et al. Charge inversion as a structural probe for C6H +5 and C6H +·6 cations. J Am Soc Mass Spectrom 10, 878–882 (1999). https://doi.org/10.1016/S1044-0305(99)00046-X

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(99)00046-X

Keywords

Search

Navigation