Advertisement

Activation of C-H and C-C Bonds in Alkanes by Heterodinuclear Metal Cluster Ions in the Gas Phase

  • Y. Huang
  • S. W. Buckner
  • B. S. Freiser

Abstract

We report on the special reactivity of RhFe+, RhCo+, and LaFe+ with alkanes and oxygen containing compounds. These three clusters are the first hetero-dinuclear transition metal cluster ions observed to activate C-H and C-C bonds in alkanes. All three cluster ions react with alkanes larger than methane mainly via dehydrogenation. In this respect, the reactivity of RhFe+, RhCo, and LaFe is more like that of Rh+ and La+ than that of Fe+ and Co+. RhFe and RhCo show similar patterns of reactivity with multiple dehydro-genation of alkanes larger than ethane, while LaFe+ shows less extensive dehydro genat ion. n-Pentane and cyclopentane react with RhFe and RhCo to split the cluster and form RhC5H6 and RhC5H5 +, presumably the cyclopenta-diene- and cyclopentadienyl-rhodium cations. These reactions imply D°(Rh+-cyclopentadienyl)>189 kcal/mol. Other thermochemical limits are reported including D°(RhCo+-CH2)>93 kcal/mol, D°(RhFe+-CH2)>78 kcal/mol, and D°(RhFe+-benzene)>60 kcal/mol. The special reactivity is discussed in terms of reduced overlap in cluster ions containing a second or third row metal bound to a first row metal relative to clusters containing two first row metals. Finally, oxide abstraction is observed for reaction of the clusters with ethylene oxide suggesting D°(MM’+-O)>89 kcal/mol.

Keywords

Ethylene Oxide Metal Carbonyl Fourier Transform Mass Spectrometry Phase Transition Metal Mass Spectrometry Instrumentation 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1).
    Cotton, F.A.; Walton, R.A.; “Multiple Bonds Between Metal Atoms”, Wiley, 1982.Google Scholar
  2. 2).
    Smalley, R.E.; “Supersonic Cluster Beams: An Alternative Approach To Surface Science” Comparison of Ab-initio Quantum Chemistry With Experiment, R.J. Bartlett ed.,(D. Reidel Publ. Co.).Google Scholar
  3. 3).
    For a recent review of gas phase transition metal ion chemistry see: Allison, J.; Prog. Inorg. Chem.; 34 (1986).Google Scholar
  4. 4).
    Jacobson, D.B.; Freiser, B.S.; J. Am. Chem. Soc., 107, 1581 (1985).CrossRefGoogle Scholar
  5. 5).
    Freas, R.B.; Ridge, D.P.; J. Am. Chem. Soc, 102, 7129 (1980).CrossRefGoogle Scholar
  6. 6).
    Hettich, R.L.; Freiser, B.S.; J. Am. Chem. Soc., 107, 6222 (1985).CrossRefGoogle Scholar
  7. 7).
    Tews, E.C.; Lech, L.M.; Buckner, S.W.; Freiser, B.S.; in preperation.Google Scholar
  8. 8).
    Barrett, P.H.; Pasternak, M.; Pearson, R.G.; J. Am. Chem. Soc., 101, 222 (1979).CrossRefGoogle Scholar
  9. 9).
    Davis, S.C.; Klabunde, K.J.; J. Am. Chem. Soc, 100, 5974 (1978).CrossRefGoogle Scholar
  10. 10).
    Davis, S.C.; Severson, S.J.; Klabunde, K.J.; J. Am. Chem. Soc., 103, 3024 (1981).CrossRefGoogle Scholar
  11. 11).
    Freas, R.B.; Ridge, D.P.; J. Am. Chem. Soc., 106, 825 (1984).CrossRefGoogle Scholar
  12. 12).
    Jacobson, D.B.; Freiser, B.S.; J. Am. Chem. Soc., 106, 5351 (1984).CrossRefGoogle Scholar
  13. 13).
    Cody, R.B.; Burnier, R.C.; Reents, W.D., Jr.; Carlin, T.J.; McCrery, D.A.; Lengel, R.K.; Freiser, B.S.; Int. J. Mass Spectrom. Ion Phys., 33, 37 (1980).CrossRefGoogle Scholar
  14. 14).
    Jacobson, D.B.; Freiser, B.S.; J. Am. Chem. Soc., 106, 4623 (1984).CrossRefGoogle Scholar
  15. 15).
    Comisarow, M.B.; Marshall, A.G.; J. Chem. Phys., 64, 110 (1976).ADSCrossRefGoogle Scholar
  16. 16).
    Cody, R.B.; Burnier, R.C.; Freiser, B.S.; Anal. Chem., 54, 96 (1982).CrossRefGoogle Scholar
  17. 17).
    Carlin, T.J.; Freiser, B.S.; Anal. Chem., 55, 571 (1982).CrossRefGoogle Scholar
  18. 18).
    Ahmed, M.S.; Dunbar, R.C.; “Collisional Ouenching of Photo-Excited Bromobenzene Ions”; presented at the 34th Annual Conference on Mass Spectrometry and Allied Topics, Cincinnati, OH, June 8–13, 1986.Google Scholar
  19. 19).
    Byrd, G.D.; Freiser, B.S.; J. Am. Chem. Soc., 104, 5944 (1982).CrossRefGoogle Scholar
  20. 20).
    Huang, Y.; Freiser, B.S.; Organometallics, submitted.Google Scholar
  21. 21).
    Byrd, G.D.; Burnier, R.C.; Freiser, B.S.; J. Am. Chem. Soc., 104, 3565 (1982).CrossRefGoogle Scholar
  22. 22).
    Jacobson, D.B.; Freiser, B.S.; in preparation.Google Scholar
  23. 23).
    Halle, L.F.; Klein, F.S.; Beauchamp, J.L.; J. Am. Chem. Soc., 106, 2543 (1984).CrossRefGoogle Scholar
  24. 24).
    Sallans, L.; Lane, K.R.; Squires, R.R.; Freiser, B.S.; J. Am. Chem. Soc., 107, 4379 (1985).CrossRefGoogle Scholar
  25. 25).
    Supplementary thermochemical information taken from: Rosenstock, H.M.; Draxl, D.; Steiner, B.W.; Herron, J.T.; J. Phys. Chem. Ref. Data, Suppl. I, 6, (1977).Google Scholar
  26. 26).
    Jacobson, D.B.;, Byrd, G.D.; Freiser, B.S.; Inorg. Chem., 23, 553 (1984)CrossRefGoogle Scholar
  27. 27).
    Byrd, G.D.; Ph.D. Thesis, 1982, Purdue University.Google Scholar
  28. 28).
    Jackson, T.C.; Jacobson, D.B.; Freiser, B.S.; J. Am. Chem. Soc., 106, 1252 (1984).CrossRefGoogle Scholar
  29. 29).
    Armentrout, P.B.; Halle, L.F.; Beauchamp, J.L.; J. Chem. Phys., 76, 2449 (1982).ADSCrossRefGoogle Scholar
  30. 30).
    Jacobson, D.B.; Freiser, B.S.; J. Am. Chem. Soc., 108, 27 (1986).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1987

Authors and Affiliations

  • Y. Huang
    • 1
  • S. W. Buckner
    • 1
  • B. S. Freiser
    • 1
  1. 1.Department of ChemistryPurdue UniversityW. LafayetteUSA

Personalised recommendations