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Volumn 3, Issue 11, 2005, Pages 2191-2201

Substituent effects and the role of negative hyperconjugation in siloxycarbene rearrangements

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; CONFORMATIONS; MOLECULAR STRUCTURE; OXYGEN; QUANTUM THEORY; SUBSTITUTION REACTIONS; THERMODYNAMICS;

EID: 20844456201     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/b416058d     Document Type: Article
Times cited : (5)

References (49)
  • 8
    • 20844463684 scopus 로고    scopus 로고
    • note
    • The fact that the pertinent HOMO-LUMO interactions for the 1,2-silyl migration and decarbonylation mechanisms have destabilizing antibonding components implies that the rearrangements are symmetry-forbidden.
  • 15
    • 20844439617 scopus 로고    scopus 로고
    • note
    • I is used for reactions in which there is no resonance component.
  • 17
    • 20844455361 scopus 로고    scopus 로고
    • note
    • A negative ρ value indicates that the reaction site is stabilized by electron-donating substituents.
  • 18
    • 0030453602 scopus 로고    scopus 로고
    • We note that Moss et al. interpreted the negative ρ value as indicative of an anion-like shift of the acyl group to the "vacant" carbene p orbital, an interpretation that contradicted their ab initio findings: R. A. Moss, S. Xue, W. Liu and K. Krogh-Jespersen, J. Am. Chem. Soc., 1996, 118, 12588.
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 12588
    • Moss, R.A.1    Xue, S.2    Liu, W.3    Krogh-Jespersen, K.4
  • 46
    • 0004157499 scopus 로고
    • Clarendon Press, Oxford
    • A bond critical point (BCP) is the point of minimum electronic density ρ(r) along a bond or bond path: R. F. W. Bader, Atoms in Molecules: A Quantum Theory, Clarendon Press, Oxford, 1990.
    • (1990) Atoms in Molecules: A Quantum Theory
    • Bader, R.F.W.1
  • 47
    • 20844444393 scopus 로고    scopus 로고
    • McMaster University, Canada
    • The AIMPAC suite of programs is available from Professor R. F. W. Bader, McMaster University, Canada, and from the AIMPAC website (www.chemistry. mcmaster.ca/aimpac).
    • AIMPAC website
    • Bader, R.F.W.1
  • 48
    • 20844433461 scopus 로고    scopus 로고
    • note
    • Only carbene conformers with the Si-X bond antiperiplanar to the O2-C6 bond were considered in this work.
  • 49
    • 20844463683 scopus 로고    scopus 로고
    • note
    • NBO only evaluates orbital energies and stabilization energies due to hyperconjugation if a well-defined one-electron effective Hamiltonian operator such as the Fock or Kohn-Sham operator is available. No such operator is available for correlated descriptions such as MP2.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.