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Volumn 120, Issue 14, 1998, Pages 3499-3503

Why are nitrenes more stable than carbenes? An ab initio study

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE;

EID: 0032522109     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973935x     Document Type: Article
Times cited : (65)

References (44)
  • 16
  • 23
    • 2642663951 scopus 로고    scopus 로고
    • note
    • 2 by 1.0 kcal/mol at (8,8)CASSCF/6-31G* and by 2.0 kcal/mol at (8,8)CASPT2N/6-31G*.
  • 24
    • 2642598490 scopus 로고    scopus 로고
    • note
    • 3-PyCH was chosen over 2-PyCH for detailed study because the interaction between the ring nitrogen and the divalent carbon atom is smaller in the former carbene than in the latter. For example, whereas, at the CASPT2N level, the syn and anti geometries differ in energy by only 0.3 kcal/mol in singlet 3-PyCH, they differ by 3.6 kcal/mol in singlet 2-PyCH. The greater similarity in energies of the syn and anti conformers of 3-PyCH, compared to 2-PyCH, thus makes 3-PyCH a better model for PhCH, for which the analogous conformers are degenerate.
  • 25
    • 2642693152 scopus 로고    scopus 로고
    • note
    • 3A″ states of PhCH).
  • 28
    • 0041401966 scopus 로고
    • The G2 method gives energies that are effectively equivalent to QCISD(T)/6-311+G(3df, 2p)//Full-MP2/6-31G* calculations, which are then corrected with scaled HF/6-31G* zero-point and thermal corrections to obtain enthalpies at 298 K. [Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221.]
    • (1991) J. Chem. Phys. , vol.94 , pp. 7221
    • Curtiss, L.A.1    Raghavachari, K.2    Trucks, G.W.3    Pople, J.A.4
  • 37
    • 2642594515 scopus 로고    scopus 로고
    • note
    • Since the energy of syn-3-PyCH is lower than that of the anti-3-PyCH in both the lowest singlet and triplet states, the energies computed for the syn stereoisomer are those that are reported in Table 1.
  • 38
    • 2642596538 scopus 로고    scopus 로고
    • note
    • 2.
  • 39
    • 2642685024 scopus 로고    scopus 로고
    • note
    • 12
  • 40
    • 2642691145 scopus 로고    scopus 로고
    • note
    • 2 should indeed be stronger than an N-H bond formed by triplet NH.
  • 41
    • 0003363438 scopus 로고    scopus 로고
    • Neutral Thermochemical Data
    • Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD 20899, August 1997
    • (a) Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD 20899, August 1997 (http://webbook.nist.gov).
    • NIST Standard Reference Database Number 69
    • Afeefy, H.Y.1    Liebman, J.F.2    Stein, S.E.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.