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Volumn 110, Issue 22, 2006, Pages 7237-7246

Butatrienes as extended alkenes: Barriers to internal rotation and substitution effects on the stabilities of the ground states and transition States

Author keywords

[No Author keywords available]

Indexed keywords

BUTATRIENE; INTERNAL ROTATION; TRANSITION (TS) STATES;

EID: 33745508561     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0607770     Document Type: Article
Times cited : (26)

References (111)
  • 25
    • 33745509829 scopus 로고    scopus 로고
    • Gilbert, A., Baggott, J., Eds. CRC Press: Boca Raton
    • Gilbert, A., Baggott, J., Eds. Essentials of Molecular Photochemistry; CRC Press: Boca Raton, 1991.
    • Essentials of Molecular Photochemistry , pp. 1991
  • 48
    • 0037862197 scopus 로고
    • (a) Kerr, J. A. Chem. Rev. 1966, 66, 465-500.
    • (1966) Chem. Rev. , vol.66 , pp. 465-500
    • Kerr, J.A.1
  • 70
    • 33745495121 scopus 로고
    • (E. I. Dupont de Nemours, Wilmington DE) U.S Patent 2, 136, 178
    • Carothers, W. H.; Berchet, G. J. (E. I. Dupont de Nemours, Wilmington DE) U.S Patent 2, 136, 178, 1937.
    • (1937)
    • Carothers, W.H.1    Berchet, G.J.2
  • 76
    • 33745483188 scopus 로고    scopus 로고
    • Chynwat, V. Ph.D. Thesis, Worcester Polytechnic Institute, 1992
    • Chynwat, V. Ph.D. Thesis, Worcester Polytechnic Institute, 1992.
  • 90
    • 0346047571 scopus 로고    scopus 로고
    • Neutral thermochemical data
    • NIST Standard Reference Database Number 69; Linstrom, P. J., Mallard, W. G., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 20899; March
    • Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Chemistry WebBook; NIST Standard Reference Database Number 69; Linstrom, P. J., Mallard, W. G., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 20899; March 2003 (http://webbook.nist.gov).
    • (2003) NIST Chemistry WebBook
    • Afeefy, H.Y.1    Liebman, J.F.2
  • 105
    • 33745507416 scopus 로고    scopus 로고
    • note
    • 2 fragments is 173 kcal/mol. Subtracting the value for the rotational barrier in ethylene (65 kcal/mol) leaves a σ-bonding energy of 108 kcal/mol. This value is larger than the bond strength in ethane of 90 kcal/mol, as to be expected on the basis of hybridization arguments. However, a better estimate of the π-bonding in ethylene corrects for the significant hyperconjugative stabilization presented above. The hypercon-jugative stabilization is added to the rotational barrier (65 + 14.7 kcal/mol = 79.7 kcal/mol), and this is subtracted from the BDE of ethylene yielding a σ-bonding energy of 93.3 kcal/mol, only slightly larger than the bond energy in ethane.
  • 106
    • 33745491214 scopus 로고    scopus 로고
    • note
    • This is a simplistic method, since it assumes that the hyperconjugative contribution in the transition state to rotation of ethylene does not change for the substituted species. A few reasons to expect some change are differences in C-C vs C-H hyperconjugative stabilization and changes in bond lengths and angles.
  • 110


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