View PDF Version
 
DOI: 10.1039/A900379G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 1459-1464

Nature of the transition state in gas phase SN2 identity reactions: correlation between nucleophilicity and proton affinity

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

Einar Uggerud

Abstract

The potential energy profiles of the cationic: A + CH3A+→+ACH3 + A (A = NH3, H2O, HF), and anionic: A– + CH3A→ACH3 + A– (A– = NH2–, OH–, F–) SN2 reactions were obtained using quantum chemical methods [MP2, G2, CCSD(T)]. A linear rate–energy relationship in the form of a correlation between the critical energy, ΔE[hair space] diff, and the proton affinity of A was found within subgroups of similar nucleophiles (NH3, H2O, HF; NH2–, OH–, F– ; F–, Cl–, Br–, I–). The analysis shows that the different susceptibility for each class is due to properties of the transition structures alone, and not of the reactants.

References

  1. W. P. Jencks, Chem. Rev., 1985, 85, 511 CrossRef CAS.
  2. J. N. Brønsted and K. J. Pedersen, Z. Phys. Chem., 1924, 108, 185 CAS.
  3. L. P. Hammett, J. Am. Chem. Soc., 1937, 59, 96 CrossRef CAS.
  4. C. G. Swain and C. B. Scott, J. Am. Chem. Soc., 1953, 75, 141 CrossRef CAS.
  5. C. K. Ingold and E. Rothstein, J. Chem. Soc., 1928, 1217 RSC.
  6. C. K. Ingold, Structure and Mechanism in Organic Chemistry, Cornell University Press, Ithaca, New York, 1955 Search PubMed.
  7. N. Isaacs, Physical Organic Chemistry, Longman Scientific & Technical, Burnt Hill, Harlow, Essex, UK, 1995 Search PubMed.
  8. T. H. Lowry and K. S. Richardson, Mechanism and Theory in Organic Chemistry, Harper & Row, New York, 1981 Search PubMed.
  9. J. March, Advanced Organic Chemistry, John Wiley & Sons, New York, 1985 Search PubMed.
  10. M. L. Chabinyc, S. L. Craig, C. K. Regan and J. I. Brauman, Science, 1998, 279, 1882 CrossRef CAS.
  11. Nucleophile, from lat. nucleus, dim. of nux nucis nut, kernel and gr. philos, friend, to love. The ability of an attacking group A to accommodate nucleophilic displacement in an SN2 reaction. A quantitative measure of this is obtained from linear free energy relationships determined from the rates of substitution in the series of reactions, A + R–B→R–A + B, where the nucleofuge B is kept constant (IUPAC).
  12. Nucleofuge, from lat. nucleus, dim. of nux nucis nut, kernel and lat. fuga bring to fly. The ability of a leaving group B to accommodate nucleophilic displacement in an SN2 reaction (IUPAC).
  13. D. K. Bohme and L. B. Young, J. Am. Chem. Soc., 1970, 92, 7354 CrossRef CAS.
  14. D. K. Bohme and A. B. Raksit, J. Am. Chem. Soc., 1984, 106, 3447 CrossRef CAS.
  15. K. Tanaka, G. I. MacKay, J. D. Payzant and D. K. Bohme, Can. J. Chem., 1976, 54, 1643 CAS.
  16. W. E. Farneth and J. I. Brauman, J. Am. Chem. Soc., 1976, 98, 5546 CrossRef CAS.
  17. D. K. Bohme and G. I. Mackay, J. Am. Chem. Soc., 1981, 103, 978 CrossRef CAS.
  18. W. N. Olmstead and J. I. Brauman, J. Am. Chem. Soc., 1977, 99, 4219 CrossRef CAS.
  19. W. N. Olmstead and J. I. Brauman, J. Am. Chem. Soc., 1979, 101, 3715 CrossRef CAS.
  20. G. Caldwell, T. F. Magnera and P. Kebarle, J. Am. Chem. Soc., 1984, 106, 959 CrossRef CAS.
  21. C. H. DePuy, S. Gronert, A. Mullin and V. M. Bierbaum, J. Am. Chem. Soc., 1990, 112, 8650 CrossRef CAS.
  22. E. P. F. Lee, J. M. Dyke and C. A. Mayhew, J. Phys. Chem. A, 1998, 102, 8349 CrossRef CAS.
  23. K. Hiraoka and P. Kebarle, J. Am. Chem. Soc., 1976, 98, 6119 CrossRef CAS.
  24. K. Hiraoka and P. Kebarle, J. Am. Chem. Soc., 1977, 99, 360 CrossRef CAS.
  25. K. Hiraoka and P. Kebarle, Can. J. Chem., 1980, 58, 2262 CAS.
  26. K. Hiraoka, H. Takimoto and K. Morise, J. Am. Chem. Soc., 1986, 108, 5683 CrossRef CAS.
  27. J. M. S. Henis, J. Am. Chem. Soc., 1968, 90, 844 CrossRef.
  28. J. L. Beauchamp and M. C. Caserio, J. Am. Chem. Soc., 1972, 94, 2638 CrossRef CAS.
  29. J. L. Beauchamp, M. C. Caserio and T. B. McMahon, J. Am. Chem. Soc., 1974, 96, 6243 CrossRef CAS.
  30. T. B. McMahon and J. L. Beauchamp, J. Phys. Chem., 1977, 81, 593 CrossRef CAS.
  31. Z. Karpas and M. Meot-Ner, J. Phys. Chem., 1989, 93, 1859 CrossRef CAS.
  32. L. M. Bass, R. D. Cates, M. F. Jarrold, N. J. Kirchner and M. T. Bowers, J. Am. Chem. Soc., 1983, 105, 7024 CrossRef CAS.
  33. J. C. Kleingeld and N. N. M. Nibbering, Org. Mass Spectrom., 1982, 17, 136 CAS.
  34. E. Uggerud and L. Bache-Andreassen, Chem. Eur. J., 1999, in the press Search PubMed.
  35. S. Wolfe, D. J. Mitchell and H. B. Schlegel, J. Am. Chem. Soc., 1981, 103, 7692 CrossRef CAS.
  36. S. Wolfe, D. J. Mitchell and H. B. Schlegel, J. Am. Chem. Soc., 1981, 103, 7694 CrossRef CAS.
  37. S. S. Shaik, H. B. Schlegel and S. Wolfe, Theoretical Aspects of Physical Organic Chemistry: The SN2 Reaction, John Wiley & Sons, New York, 1992 Search PubMed.
  38. Z. Shi and R. J. Boyd, J. Am. Chem. Soc., 1990, 112, 6789 CrossRef CAS.
  39. Z. Shi and R. J. Boyd, J. Am. Chem. Soc., 1991, 113, 2434 CrossRef CAS.
  40. Z. Shi and R. J. Boyd, J. Am. Chem. Soc., 1991, 113, 1072 CrossRef CAS.
  41. W. Hase, Science, 1994, 266, 1994.
  42. F. Jensen, Chem. Phys. Lett., 1992, 196, 368 CrossRef CAS.
  43. S. Gronert, J. Am. Chem. Soc., 1993, 115, 652 CrossRef CAS.
  44. I. Lee, C. H. Kim and B.-S. Lee, J. Phys. Org. Chem., 1995, 8, 473 CAS.
  45. P. Botschwina, Theor. Chem. Acc., 1998, 99, 426 CrossRef CAS.
  46. “Atter og fram, det er lige langt; ud og ind, det er lige trangt”(“Backwards and forwards, it's just as far; out or in, it's just as narrow”) from H. Ibsen: Peer Gynt, act 2, Gyldendalske boghandel (F.Hegel), København, 1867(english translation by P.Watts, Penguin Books, London, 1966) Search PubMed.
  47. J. A. Dodd and J. I. Brauman, J. Am. Chem. Soc., 1984, 106, 5356 CrossRef CAS.
  48. B. D. Wladkowski and J. L. Brauman, J. Phys. Chem., 1993, 97, 13158 CrossRef CAS.
  49. E. Uggerud, Int. J. Mass Spectrom., 1999, 182/183, 13 CrossRef.
  50. K. Morokuma, J. Am. Chem. Soc., 1982, 104, 3732 CrossRef CAS.
  51. K. Raghavachari, J. Chandrasekhar and R. C. Burnier, J. Am. Chem. Soc., 1984, 106, 3124 CrossRef CAS.
  52. M. N. Glukhovtsec, J. E. Szulejko, T. B. McMahon, J. W. Gauld, A. P. Scott, B. J. Smith, A. Pross and L. Radom, J. Phys. Chem., 1994, 98, 13099 CrossRef.
  53. M. N. Glukhovtsec, A. Pross, H. B. Schlegel, R. D. Bach and L. Radom, J. Am. Chem. Soc., 1996, 118, 11258 CrossRef.
  54. Z. D. Hamou-Tara, E. Kassab, M. Allavena and E. M. Evleth, Chem. Phys. Lett., 1988, 150, 86 CrossRef.
  55. GAUSSIAN 94, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Peterson, J. A. Mongomery, 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. Reploge, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Pittsburgh, PA, 1994.
  56. C. Möller and M. S. Plesset, Phys. Rev., 1934, 46, 618 CrossRef CAS.
  57. P. C. Hariharan and J. A. Pople, Theor. Chim. Acta, 1973, 28, 213 CrossRef CAS.
  58. L. A. Curtiss, K. Raghavachari, G. W. Trucks and J. A. Pople, J. Chem. Phys., 1991, 94, 7221 CrossRef CAS.
  59. R. J. Bartlett and G. D. Purvis, Int. J. Quantum Chem., 1978, 14, 516 CrossRef CAS.
  60. T. B. McMahon and P. Kebarle, Can. J. Chem., 1985, 63, 3160 CAS.
  61. J. Brauman and C.-C. Han, J. Am. Chem. Soc., 1988, 110, 5611 CrossRef CAS.
  62. T. B. McMahon, T. Heinis, G. Nicol, J. K. Hovey and P. Kebarle, J. Am. Chem. Soc., 1988, 110, 7591 CrossRef CAS.
  63. S. G. Lias, J. E. Bartmess, J. F. Liebman, J. H. Holmes, R. D. Levin and W. G. Mallard, J. Phys. Chem. Ref. Data, 1988, 17, 1.
  64. S. G. Lias, H. M. Rosenstock, K. Deard, B. W. Steiner, J. T. Herron, J. H. Holmes, R. D. Levin, J. F. Liebman, S. A. Kafafi, J. E. Bartmess and E. F. Hunter, in NIST-webbook, http://webbook.nist.goc/chemistry, 1997.
  65. S. S. Shaik, Prog. Phys. Org. Chem., 1985, 15, 197 Search PubMed.
  66. A. Pross, Adv. Phys. Org. Chem., 1985, 21, 99 CAS.
  67. J. O. Edwards, J. Am. Chem. Soc., 1954, 76, 1540 CrossRef CAS.
  68. J. O. Edwards, J. Am. Chem. Soc., 1956, 78, 1819 CrossRef CAS.
  69. R. G. Pearson and J. Songstad, J. Am. Chem. Soc., 1967, 89, 1827 CrossRef CAS.
  70. C. D. Ritchie, Can. J. Chem., 1986, 64, 2239 CAS.
  71. S. P. McManus, J. Org. Chem., 1981, 46, 635 CrossRef CAS.
  72. M. J. Pellerite and J. I. Brauman, J. Am. Chem. Soc., 1980, 102, 5993 CrossRef CAS.
  73. M. J. Pellerite and J. I. Brauman, J. Am. Chem. Soc., 1983, 105, 2672 CrossRef CAS.
  74. Nucleoaffinity, from lat. nucleus, dim. of nux nucis nut, kernel and lat. affinitas, related, lit. bordering on. The ability of a nucleofuge/nucleophile to accommodate nucleophilic displacement in the identity (narcissistic) reaction A + CH3A→CH3A + A. Defined as the negative enthalpy change of the hypothetical reaction A + CH3++ A→[A ⋯ CH3+⋯ A]. The latter species it the transition structure of the reaction (definition suggested here).
Click here to see how this site uses Cookies. View our privacy policy here.