Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

MNDO Studies on the Gas-Phase S$_N$2 Reaction$^*$

  • Published : 1985.08.20
Download PDF
⟨ Previous Next ⟩

Abstract

The MNDO was found to be the most reliable semi-empirical SCF-MO method for the studies of $S_N2$ reactions involving anion and neutral molecule. The results of our MNDO calculations on the $S_N2$ reactions of $CH_3X$ + $Y^-$ → $CH_3Y$ + X- where X = H, F, Cl, CN, $CH_3$, and Y = F, $CH_3$ showed that the order of the leaving group ability is the reverse of the order of proton affinities. It was also found that there is no symbiosis involved in the SN2 transition state and the departure of the leaving group is relatively late in contrast to the early bond formation of the nucleophile. The Marcus equation was found to apply to the MNDO barriers and energy changes.

Keywords

References

  1. Advanced Organic Chemistry F. A. Carey;R. J. Sundberg
  2. J. Am. Chem. Soc. v.103 A. Press;S. S. Shaik
  3. Kinetic and Mechanism J. W. Moore;R. C. Pearson
  4. Mechanism and Theory in Organic Chemistry T.H. Lowry;K. S. Richardson
  5. Solvent effect on Chemical Phenomena E. S. Amis;J. F. Hinton
  6. Chem. Rew. v.1 A. J. Parker
  7. J. Org. Chem. v.42 F. P. Ballistreri;E. Maccarone;G. Musumarra;G. A. Tomaselli
  8. J. Chem. Soc. E. D. Hughes;C. K. Ingold;C. S. Patel
  9. J. Chem. Soc. J. L. Gleave;E. D. Hughes;C. K. Ingold
  10. Tetrahedron. v.39 I. Lee;I. S. Koo
  11. Tetrahedron Lett. I. Lee;N. L. Kim;S. C. Sohn
  12. J. Am. Chem. Soo. v.90 E. C. F. Ko;A. J. Parker
  13. Tetrahedron Lett. I. Lee;N. L. Kim;S. C. Sohn
  14. Int. J. Mass. Spectrum Ion Phys. v.7 R. T. Mclver, Jr.;R. C. Dunbar
  15. Program No. 236, Quantum Chemistry Program Exchange W. J. Hehre;W. A. Lathan;R. Ditchfield;M. D. Newton;J. A. Pople
  16. J. Chem, Soc. v.43 D. P. Santry;G. A. Segal
  17. Theoret. Chem. Acta v.25 P. Cremaschi;A. Gamba;M. Simonetta
  18. Angew, Chem. Int. Ed. v.10 P. D. Gillespie;I. Ugi
  19. J. Am. Chem. Soc. v.94 a. Dedieu;A. Veillard
  20. J. Am. Chem. Soc. v.98 F. Keil;R. Ablrichs
  21. J. Am. Chem. Soc. v.103 S. Wolfe;D. J. Mitchell;H. B. Schlegel
  22. J. Am. Chem. Soc. v.99 M. J. S. Dewar;W. Thiel
  23. J. Am. Chem. Soc. v.93 M. J. S. Dewar;G. P. Ford;M. L. McKee;H. S. Rzepa;L. E. Wade
  24. Electrons in Chemical Reactions: First Principles L. Salem
  25. Chem. Phys. Letters. v.45 A. Komornicki;K. Ishida;K. Morokuma
  26. J. Am. Chem. Soc. v.94 J. W. Mclver, Jr.;Komornicki
  27. Theory and Practice of MO. Calculations on Organic Molecules I. G. Csizmadia
  28. J. Am. Chem. Soc. v.97 R. C. Bingham;M. J. S. Dewar;D. H. Lo
  29. Mechanism and Theory in Organic Chemistry T. H. Lowry;K. S. Richardson
  30. J. Am. Chem. Soc. v.85 R. G. Pearson
  31. J. Am. Chem. Soc. v.90 G. Klopman
  32. Quantum Theory of Chemical Reactions A. Dedieu;A. Veillard
  33. Angew, Chem. Int. ED. v.9 H. Kollmar;H. O. Smith
  34. J. Am. Chem. Soc. v.93 J. E. Williams;V. Buss;L. C. Allen
  35. Frontier Orbitals and Organic Chemical Reactions I. Fleming
  36. J. Comp, Chem. v.3 I. Lee;Y. G. Cheun;K. Yang
  37. J. Org. Chem. v.32 R. G. Pearson;J. Songstad
  38. Prog. Chem. and Chem. Inds v.24 I. Lee;H. K. Kang
  39. J. Am. Chem. Soc. v.103 S. Wolfe;D. J. Mitchell
  40. J. Am. Chem. Soc. v.105 J. R. Murdoch
  41. Chemical Kinetics R. E. Weston;H. A. Schwartz
  42. J. Phys. Chem. v.72 A. D. Cohen;R. A. Marcus
  43. J. Am. Chem. Soc. v.91 R. A. Marcus
  44. Pure Appl. Chem. v.51 W. J. Albery
  45. J. Am. Chem. Soc. v.101 E. S. Lewis;S. J. Kukes
  46. J. Phys. Chem. v.72 R. A. Marcus