Reply to comment on "identity hydrogen abstraction reactions, X• + H-X′ → X-H + X′• (X = X′ = CH3, SiH3, GeH3, SnH3, PbH3): A valence bond modeling"

Journal of Physical Chemistry A

Volumn 106, Issue 19, 2002, Pages 5043-5045

  Shaik, Sason ^a   De Visser, Samuël P ^a   Wu, Wei ^a   Song, Lingchun ^a   Hiberty, Philippe C ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL ACTIVATION; CHEMICAL BONDS; HYDROGEN; MOLECULAR STRUCTURE; REACTION KINETICS;

ABSTRACTION REACTIONS; BREATHING ORBITAL VALENCE BOND THEORY; POLAR EFFECTS; VALENCE BOND;

PHYSICAL CHEMISTRY;

EID: 0037118371     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp015589i     Document Type: Note

References (24)

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3. For discussion of the effect in radical addition see: Fischer, L.; Radom, R. Angew. Chem., Int. Ed. Engl. 2001, 40, 1340.
4. For a recent discussion of the importance of ionic structures in hydrogen abstractions, see: Donahue, N. M.; Clarke, J. S.; Anderson, J. G. J. Phys. Chem. A 1998, 102, 3293.
5. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 6459. The paper discusses a beautiful case in which, tertiary butoxy radical abstracts the stronger cubyl C-H bond, from methyl cubane and not the weaker methyl C-H bond, due to the "polar effect" that has its origins in the stability of cubyl cation.
6. (a) Lynch, B. J.; Fast, P. L.; Harris, M.; Truhlar, D. G. J. Phys. Chem. 2000, 104, 4812.
7. a's, which reproduce the experimental behavior. Garrett, B. C.; Truhlar, D. G.; Wagner, A. F.; Dunning, T. H., Jr. J. Chem. Phys. 1983, 78, 4400.
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11. See the same set of structures in: (a) Balint-Kurti, G. G.; Benyworth, P. R.; Davis, M. J.; Williams, I. H. J. Phys. Chem. 1992, 96, 4346.
12. (b) Malcolm, N. O. J.; McDouall, J. J. W. J. Phys. Chem. 1994, 98, 12579.
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18. Shaik, S. S. In New Concepts for Understanding Chemical reactions; Bertran, J., Csizmadia, I. G., Eds.; ASI NATO Series, C267; Kluwer Publishers: Dordrecht, The Netherlands, 1989; p. 165.
19. Malrieu, J. P. Nouv. J. Chim. 1986, 126, 61.
20. Wu, W.; Danovich, D.; Shurki, A.; Shaik, S. J. Phys. Chem. A 2000, 104, 8744.
21. For conclusions regarding the failure of BEBO in some hydrogen abstraction reactions: Dunning, T. H. J. Phys. Chem. 1984. 88, 2469.
22. Shaik, S,; Shurki, A.; Danovich, D.; Hiberty, P. C. Chem. Rev. 2001. 101, 1501.
23. (a) Our calculation, which are at the highest level so far, UCCSD(T)/6-311++G(3df,3pd)//RCCSD(T)/6-311++G(3df,3pd), leads to a barrier of 17.8 kcal/mol (FHF angle = 132.6°). At the same level, the barrier for a constrained linear TS is 20.9 kcal/mol. The barrier calculated at the UCCSD(T)/6-31++G**//QCISD/6-31G** is 19.1 kcal/mol (FHF angle = 128.3°). A barrier of 17.5 kcal/mol, at the QCISD(T)/D95++(3df,2p) is reported in: Fox, G. L.; Schlegel, H. B. J. Am. Chem. Soc. 1993, 115, 6870.
24. (b) A previous datum of 23.9 kcal/mol is reported in: O'Neil, S. V.; Schaefer, H. F., III.; Bender, C. F. Proc. Natl. Acad. Sci. U.S.A. 1974, 71, 104.