Carbene rearrangements unsurpassed: Details of the C7H6 potential energy surface revealed

Journal of Organic Chemistry

Volumn 61, Issue 20, 1996, Pages 7030-7039

  Schreiner, Peter R ^a,b   Karney, William L ^c,d   Schleyer, Paul Von Ragué ^a,b   Borden, Westen Thatcher ^c   Hamilton, Tracy P ^e   Schaefer III, Henry F ^b  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^b UNIVERSITY OF GEORGIA   (United States)

^c UNIVERSITY OF WASHINGTON   (United States)

^d UNIVERSITY OF SAN FRANCISCO   (United States)

^e UNIVERSITY OF ALABAMA AT BIRMINGHAM   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000827672     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960884y     Document Type: Article

References (117)

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5. This topic has been reviewed extensively; see, inter alia (a) Wentrup, C. Top. Curr. Chem. 1976, 62, 173. (b) Jones, W. M. Acc. Chem. Res. 1977, 10, 353. (c) Jones, W. M.; Brinker, U. H. In Pericyclic Reactions; Marchand, A. P., Lehr, A. E., Eds.; Academic: New York, 1977; Vol. 1, Chapter 3. (d) Wentrup, C. In Reactive Intermediates; Ambramovich, R., Ed.; Plenum: New York, 1980; Vol. 1, Chapter 4. (e) Wentrup, C. Reactive Molecules; Wiley-Interscience: New York, 1984; pp 220, 242. (f) Moss, R. A.; Jones, M., Jr. Reactive Intermediates; Wiley: New York, 1985; Vol. 3, p 91. (g) Jones, W. M. In Rearrangements in Ground and Excited States; De Mayo, P., Ed.; Academic: New York, 1980; Vol. 1, Chapter 3. (h) Wentrup, C. In Methoden der Organischen Chemie (Houben-Weyl); Regitz, M., Ed.; Thieme: Stuttgart, 1989; Vol. E19b, p 824 ff.
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115. For other examples of violations of Hund's rule in organic molecules, see: Borden, W. T.; Iwamura, H.; Berson, J. A. Acc. Chem. Res. 1994, 27, 109.
116. 1-4 (hartrees): CASSCF(8,8)/6-31G* -268.49785; CASSCF(8,8)/cc-pVDZ -268.51816; CASPT2N/6-31G* -269.31144; CASPT2N/cc-pVDZ -269.34446.
117. 2, followed by intersystem crossing and vibrational relaxation, would provide a low energy pathway for the lowest triplet state of 4 to reach the equilibrium geometry of 3.