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Volumn 939, Issue 1-3, 2010, Pages 53-58

Ring contraction mechanisms in substituted cyclohexylium cations

Author keywords

DFT; Electron donating; Electron withdrawing; Isomerization; Ring opening

Indexed keywords


EID: 72049102881     PISSN: 01661280     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.theochem.2009.09.040     Document Type: Article
Times cited : (7)

References (19)
  • 11
    • 72049095628 scopus 로고    scopus 로고
    • Ref, 8] reports three ring expansion pathways. 20.3 kcal/mol refers to the most stable of these, and is the barrier of 1,2-dimethylcyclohexylium ↔ 1-(2-propyl)cyclopentylium
    • Ref. [8] reports three ring expansion pathways. 20.3 kcal/mol refers to the most stable of these, and is the barrier of 1,2-dimethylcyclohexylium ↔ 1-(2-propyl)cyclopentylium.
  • 13
    • 72049083524 scopus 로고    scopus 로고
    • QCISD(T)/CBS(QCISD)//QCISD/6-311++Gd, p, see Ref, 9] for details
    • QCISD(T)/CBS(QCISD)//QCISD/6-311++G(d, p), see Ref. [9] for details.
  • 14
    • 72049085576 scopus 로고    scopus 로고
    • Gaussian 03, Revision C.02, M.J. Frisch et al., Gaussian, Inc., Wallingford, CT, 2004.
    • Gaussian 03, Revision C.02, M.J. Frisch et al., Gaussian, Inc., Wallingford, CT, 2004.
  • 15
    • 72049121244 scopus 로고    scopus 로고
    • There are also a further two isomers of 3a, not shown, that are related to structures 3-IV and 3-VI but with different C{single bond}C bond lengths in the cyclohexyl ring. We have been unable to connect these two isomers to the reaction pathway, and all attempts to find transition states involving these structures results in relaxation to either 3-IV or 3-VI. Calculations using B3LYP and B971 functionals on these superfluous structures results in direct relaxation to 3-IV and 3-VI motifs
    • There are also a further two isomers of 3a, not shown, that are related to structures 3-IV and 3-VI but with different C{single bond}C bond lengths in the cyclohexyl ring. We have been unable to connect these two isomers to the reaction pathway, and all attempts to find transition states involving these structures results in relaxation to either 3-IV or 3-VI. Calculations using B3LYP and B971 functionals on these superfluous structures results in direct relaxation to 3-IV and 3-VI motifs.
  • 19
    • 72049091516 scopus 로고    scopus 로고
    • NBO analysis on the transition states involved in this reaction, and similar reactions, shows no interaction between the F lone-pair and empty p-orbital on the cationic carbon. This may be due to the delocalization of the charge involved in such structures, since scrutiny of the geometries clearly indicates that such an interaction is evident
    • NBO analysis on the transition states involved in this reaction, and similar reactions, shows no interaction between the F lone-pair and empty p-orbital on the cationic carbon. This may be due to the delocalization of the charge involved in such structures, since scrutiny of the geometries clearly indicates that such an interaction is evident.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.