View PDF Version
 
DOI: 10.1039/A608011A (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1997, 93, 1881-1883

Absolute proton affinity and basicity of the carbenes CH2, CF2, CCl2, C(OH)2, FCOH, CPh2 and fluorenylidene

(Note: The full text of this document is currently only available in the PDF Version )

Josefredo R. Pliego Jr. and Wagner B. De Almeida

Abstract

Ab initio molecular orbital calculations were performed in order to determine the absolute proton affinity and basicity of some carbenes. For the species CH2, CF2, CCl2 C(OH)2, and FCOH, the G2(MP2) method was utilized, and we have obtained the values 207.0, 177.4, 209.6, 217.3 and 199.9 kcal mol-1, respectively, for the absolute proton affinities. For CPh2 and fluorenylidene the calculation was performed at the HF/DZ+(P)//HF/DZ and MP2/DZ//HF/DZ levels of theory. For CPh2 we have obtained an absolute proton affinity of 275.0 kcal mol-1 and, for fluorenylidene, the value is 272.4 kcal mol-1. The implication of these results for the carbene reaction mechanism with OH groups is discussed.

References

  1. W. Kirmse, Carbene Chemistry, Academic Press, New York, 1964 Search PubMed.
  2. J. J. Zupancic, P. B. Crase, S. C. Lapin and G. B. Schuster, Tetrahedron, 1985, 41, 1471 CrossRef CAS.
  3. D. Bethell, A. R. Newall and D. Whittaker, J. Chem. Soc. B, 1971, 23 RSC.
  4. W. Kirmse, K. Loosen and H. D. Sluma, J. Am. Chem. Soc., 1981, 103, 5935 CrossRef CAS.
  5. D. Griller, M. T. H. Liu and J. C. Scaiano, J. Am. Chem. Soc., 1983, 104, 5849.
  6. W. Kirmse, J. Killan and S. Steenken, J. Am. Chem. Soc., 1990, 112, 6399 CrossRef CAS.
  7. J. E. Chateauneuf, J. Chem. Soc., Chem. Commun., 1991, 1437 RSC.
  8. X. Du, H. Fan, J. L. Goodman, M. A. Kesselmayer, K. Krogh-Jespersen, J. A. La Villa, R. A. Moss, S. Shen and R. S. Sheridan, J. Am. Chem. Soc., 1990, 112, 1920 CrossRef CAS.
  9. J. A. Pople, K. Raghavachari, M. J. Frish, J. S. Binkley and P. V. R. Schleyer, J. Am. Chem. Soc., 1983, 105, 6389 CrossRef CAS.
  10. S. P. Walch, J. Chem. Phys., 1993, 98, 3163 CrossRef CAS.
  11. C. Gonzalez, A. Restrepo-Cossio, M. Marquez and K. B. Wiberg, J. Am. Chem. Soc., 1996, 118, 5408 CrossRef CAS.
  12. J. R. Pliego Jr. and W. B. De Almeida, Chem. Phys. Lett., 1996, 249, 136 CrossRef.
  13. J. R. Pliego Jr. and W. B. De Almeida, J. Phys. Chem., 1996, 100, 12410 CrossRef.
  14. L. A. Curtiss, K. Raghavachari and J. A. Pople, J. Chem. Phys., 1993, 98, 1293 CrossRef CAS.
  15. GAUSSIAN 94, revision D.2, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Pittsburgh PA, 1995.
  16. S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes, R. D. Levin and W. G. Mallard, J. Phys. Chem. Ref. Data, 1988, 17, suppl. 1.
  17. J. Vogt and J. L. Beauchamp, J. Am. Chem. Soc., 1975, 97, 6682 CrossRef CAS.
  18. B. A. Levi, R. W. Taft and W. T. Hehre, J. Am. Chem. Soc., 1977, 99, 8454 CrossRef CAS.
  19. C. Y. Ng, D. J. Trevor, P. W. Tiedemann, S. T. Ceyer, P. L. Kronebusch, B. H. Mahan and Y. T. Lee, J. Chem. Phys., 1977, 67, 4235 CrossRef CAS.
  20. S. T. Ceyer, P. W. Tiedemann, B. H. Mahan and Y. T. Lee, J. Chem. Phys., 1979, 70, 14 CrossRef CAS.
  21. C. Lee, G. Fitzgerald, M. Planas and J. J. Novoa, J. Phys. Chem., 1996, 100, 7398 CrossRef CAS.
  22. C. Hillebrand, M. Klessinger, M. Eckert-Maksic and Z. B. Maksic, J. Phys. Chem., 1996, 100, 9698 CrossRef CAS.
  23. D. A. Dixon and A. J. Arduengo III, J. Phys. Chem., 1991, 95, 4180 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.