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Volumn 125, Issue 31, 2003, Pages 9343-9358

Study of the chemistry of ortho- and para-biphenylnitrenes by laser flash photolysis and time-resolved IR experiments and by B3LYP and CASPT2 calculations

Author keywords

[No Author keywords available]

Indexed keywords

LASER BEAM EFFECTS; MOLECULAR VIBRATIONS; PHOTOLYSIS; PROBABILITY DENSITY FUNCTION;

EID: 0042703203     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0351591     Document Type: Article
Times cited : (91)

References (66)
  • 4
    • 0011330068 scopus 로고
    • Scriven, E. F. U., Ed.; Academic Press, New York
    • (a) Smith, P. A. S. In Azides and Nitrenes; Scriven, E. F. U., Ed.; Academic Press: New York, 1984; p 95.
    • (1984) Azides and Nitrenes , pp. 95
    • Smith, P.A.S.1
  • 22
    • 0000994578 scopus 로고    scopus 로고
    • Brinker, U. H., Ed.; Elsevier: Amsterdam
    • (b) Karney, W. L.; Borden, W. T. In Advances in Carbene Chemistry; Brinker, U. H., Ed.; Elsevier: Amsterdam, 2001; Vol. 3, pp 206-251.
    • (2001) Advances in Carbene Chemistry , vol.3 , pp. 206-251
    • Karney, W.L.1    Borden, W.T.2
  • 23
    • 0042307029 scopus 로고    scopus 로고
    • Moss, R. A., Platz, M. S., Jones M., Jr., Eds.; Wiley: New York; in press
    • (c) Platz, M. S. In Contemporary Reactive Intermediates; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley: New York, 2003; in press.
    • (2003) Contemporary Reactive Intermediates
    • Platz, M.S.1
  • 24
    • 0041806190 scopus 로고    scopus 로고
    • Moss, R. A., Platz, M. S., Jones M., Jr., Eds.; Wiley: New York; in press
    • (d) Borden, W. T. In Contemporary Reactive Intermediates; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley: New York, 2003; in press.
    • (2003) Contemporary Reactive Intermediates
    • Borden, W.T.1
  • 34
    • 0041806191 scopus 로고    scopus 로고
    • note
    • The B3LYP/6-31G* energies of 5 and 6, relative to the UB3LYP energy of 1c, are given in Table 1. The B3LYP energies of the transition structures connecting 5 and 6 to 1b are given in the Supporting Information.
  • 40
    • 0033449808 scopus 로고    scopus 로고
    • Lipkowitz, K. B., Boyd, D. B., Eds.; Wiley-VCH Publishers: New York
    • See, for example: Bally, T.; Borden, W. T. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; Wiley-VCH Publishers: New York, 1999; Vol. 13, pp 1-97.
    • (1999) Reviews in Computational Chemistry , vol.13 , pp. 1-97
    • Bally, T.1    Borden, W.T.2
  • 52
    • 0042808172 scopus 로고    scopus 로고
    • note
    • It is possible that this deviation from linearity involves a change in mechanism. For example, a 1,5-hydrogen shift at higher temperature might be replaced by a catalyzed process with not only a lower enthalpy of activation, but also with a much more negative entropy of activation. Alternatively, a contribution from tunneling to the 1,5-hydrogen shift reaction that forms 9 from 4 could be responsible for the deviation from linearity seen in Figure 14A. This interpretation has precedent in the work of Truhlar and co-workers. Furthermore, Shizuka et al. have reported experimental and theoretical evidence for tunneling during their study of a similar 1,5-hydrogen shift in the photorearranged intermediate formed from N-acetylpyrrole. However, the very small H/D kinetic isotope effect of less than 3 at low temperatures does not seem to be consistent with a mechanism involving temperature-independent tunneling below 220 K.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.