Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Theoretical Studies on the Hydrogen Atom Transfer Reaction (Ⅱ)$^*$

  • Published : 1985.12.20
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Abstract

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

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References

  1. Int. J. Quantum Chem. v.26 S. Bohm;J. Kuthan
  2. J. Am. Chem. Soc. v.106 J. Clark;G.W. spitznagel;R. Klose;R. Schleyer
  3. J. Am. Chem. Soc. v.94 A.A. Zavitas;J.A. Pinto
  4. Electrons in Chemical Reaction: First Principle L. Salem
  5. Mechanism and Theory in Organic Chemistry T.H. Lowry;K.S. Richardson
  6. J. Am. Chem. Soc. v.105 J.R. Murdoch
  7. Annu. Rew. Phys. Chem. v.15 R.A. Marcus
  8. J. Am. Chem. Soc. v.94 J.R. Murdoch
  9. J. Am. Chem. Soc. v.104 J.R. Murdoch;D.E. Magnoli
  10. J. Phys. Chem. v.67 R.A. Marcus
  11. J. Phys. Chem. v.72 A.D. Cohen;R.A. Marcus
  12. J. Am. Chem. Soc. v.91 R.A. Marchs
  13. Acc. Chem. Res. v.8 A.J. Kresge
  14. Annu. Rev. Phys. Chem. v.31 W.J. Albery
  15. Pure Appl. Chem. v.51 W.J. Albery
  16. Adv. Phys. Org. Chem. v.16 E.S. Lewis;A.J. Albery;M.M. Kreevoy
  17. J. Am. Chem. Soc. v.101 S.J. Kukes
  18. J. Am. Chem. Soc. v.103 S. Wolfe;D.J. Mitchell;H.B. Schlegel
  19. J. Am. Chem. Soc. v.102 M.J. Pellerite;J.I. Brauman
  20. J. Am. Chem. Soc. v.105 M.J. Pellerite;J.I. Brauman
  21. J. Am. Chem. Soc. v.106 J.A. Dodd;J.I. Brauman
  22. Free Radical W.A. Pryor
  23. Tetrahedron Lett. v.23 S.S. Kim;S.S. Sohn
  24. J. Am. Chem. Soc. v.97 A.A. Zavitas;A.A. Melikian
  25. J. Am. Chem. Soc. v.99 R.P. Gillon
  26. J. Am. Chem. Soc. v.103 D. Griller;F.P. Lossing
  27. J. Comput. Chem. B-S. Lee;I. Lee;C.H. Song;J.Y. Choi
  28. J. Am. Chem. Soc. v.97 R.C. Bingham;M.J.S. Dewar;D.H. Lo
  29. J. Am. Chem. Soc. v.93 M.J.S. Dewar;G.P. Ford;M.L. McKee;H.S. Rzepa;L.E. Wade
  30. Electrons in Chemical Reaction: First Principle L. Salmen
  31. Angew. Chem. v.19 K. Muller
  32. J. Comput. Chem. v.5 R.D. Gilliom
  33. J. Am. Chem. Soc. v.94 J.W. Mclver Jr.;A. Komornicki
  34. J. Am. Chem. Soc. v.103 D. Giller;F.P. Lossing
  35. Chem. Phys. Letters. v.70 M.J. Rothman;L.L. Lohr Jr.
  36. Electrons in Chemical Reaction: First Principles L. Salem
  37. J. Am. Chem. Soc. v.99 N.D. Epiotis;R.L. Yates;J.R. Larson;C.R. Kirmaier;F. Bernardi
  38. J. Am. Chem. Soc. v.100 J.R. Larson;N.D. Epiotis;F. Bernardi
  39. J. Am. Chem. Soc. v.103 A. Pross;L. Radom
  40. Acc. Chem. Res. v.4 R. Hoffmann
  41. J. Comput. Chem. v.3 I. Lee;Y.G. Cheun;K. Yang
  42. Helv. Chim. Acta. v.53 J.R. Swenson;R. Hoffman
  43. Tetrahedron I. Lee;K. Yang;H.S. Kim
  44. Structural Theory of Organic Chemistry N.D. Epiotis;W.R. Cherry;S. Shaik;R. Yates;F. Bernardi
  45. Quantum Chemistry I.N. Levine