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Volumn 126, Issue 40, 2004, Pages 12977-12983

Leaving group effects in gas-phase substitutions and eliminations

Author keywords

[No Author keywords available]

Indexed keywords

DATA REDUCTION; REACTION KINETICS; SUBSTRATES;

EID: 5644243004     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja047002u     Document Type: Article
Times cited : (48)

References (38)
  • 6
    • 0035246350 scopus 로고    scopus 로고
    • The following recent review highlights the accomplishments of many workers in the study of gas-phase substitution and elimination reactions: Gronert, S. Chem. Rev. 2001, 101, 329.
    • (2001) Chem. Rev. , vol.101 , pp. 329
    • Gronert, S.1
  • 15
    • 0041835195 scopus 로고
    • Although alkyl trifluoroacetates are known to undergo nucleophilic acyl substitution reactions in the gas phase, that process would be endothermic with a carboxylate as the nucleophile and therefore is not competitive in this system: McDonald, R. N.; Chowdhury, A. K. J. Am. Chem. Soc. 1982, 104, 901.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 901
    • McDonald, R.N.1    Chowdhury, A.K.2
  • 16
    • 0003363436 scopus 로고    scopus 로고
    • Negative ion energetics data
    • Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD
    • Bartmess, J. E. Negative Ion Energetics Data. In NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 2004; http://webbook.nist.gov.
    • (2004) NIST Standard Reference Database Number 69
    • Bartmess, J.E.1
  • 17
    • 85039501907 scopus 로고    scopus 로고
    • note
    • 3 bond than a C-Br bond).
  • 18
    • 4544285042 scopus 로고    scopus 로고
    • Neutral thermochemical data
    • Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD
    • Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Chemistry WebBook, NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 2004; http://webbook.nist.gov.
    • (2004) NIST Chemistry WebBook, NIST Standard Reference Database Number 69
    • Afeefy, H.Y.1    Liebman, J.F.2    Stein, S.E.3
  • 27
    • 0001810835 scopus 로고
    • Bowers, M. T., Ed.; Academic Press: New York
    • Su, T.; Bowers, M. T. In Gas-Phase Ion Chemistry; Bowers, M. T., Ed.; Academic Press: New York, 1979; pp 1, 83.
    • (1979) Gas-Phase Ion Chemistry , pp. 1
    • Su, T.1    Bowers, M.T.2
  • 32
    • 85039499785 scopus 로고    scopus 로고
    • note
    • The low E2 rate for ethyl iodide adds some uncertainty to the ratios. It is possible that some of the observed proton-transfer products with ethyl iodide result from reaction with a small HI impurity rather than from an E2 reaction with ethyl iodide. Therefore, the true E2 rate with ethyl iodide could be smaller and thus all of the rate ratios proportionally larger.
  • 34
    • 85039489086 scopus 로고    scopus 로고
    • note
    • N2 barrier is marginally smaller (1-2 kcal/mol) than the E2 barrier. See ref 35.
  • 36
    • 85039488039 scopus 로고    scopus 로고
    • note
    • We were not able to test this level thoroughly in these systems. It may be satisfactory, but it is possible that higher levels would be needed to obtain data that is consistent with all the iodide experiments.


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