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Volumn 105, Issue 32, 2001, Pages 7579-7587

CH2 + CO2 → CH2O + CO, one-step oxygen atom abstraction or addition/fragmentation via α-lactone?

Author keywords

[No Author keywords available]

Indexed keywords

FRAGMENTATIONS; SPIN STATE;

EID: 0035899124     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp003510o     Document Type: Article
Times cited : (23)

References (56)
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    • note
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    • Unpublished results, cited in ref 11
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    • Böhland, T.1
  • 18
    • 33751000502 scopus 로고    scopus 로고
    • note
    • Triplet carbenes: diphenylcarbene and cyclohexadienylidene; Singlet carbenes: phenyl chlorocarbene and p-nitrophenyl chlorocarbene.
  • 21
    • 33751012452 scopus 로고    scopus 로고
    • note
    • The calculations reported in ref 19 were performed using HF and CISD 3-21G+d+sp and D95+d+sp wave functions.
  • 27
    • 0011626745 scopus 로고    scopus 로고
    • note
    • Detailed geometry and energy data for the species considered are available as supporting material.
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    • Although well-defined economical methods are available for accurate calculations of carbene S-T gaps, their general extrapolation to reaction potential energy surfaces is nontrivial; see Carter, E. A.; Goddard, W. A. J. Phys. Chem. 1988, 88, 1752.
    • (1988) J. Phys. Chem. , vol.88 , pp. 1752
    • Carter, E.A.1    Goddard, W.A.2
  • 35
    • 0011693043 scopus 로고    scopus 로고
    • note
    • The active vibration, corresponding to the reaction coordinate, is indicated by the arrows. This motion leads from the TS toward the reactants or products with which it is connected on PES (see the energy profiles).
  • 36
    • 0000189651 scopus 로고
    • We used here the hybrid B3LYP functional (see Becke, A. D. J. Chem. Phys. 1993, 98, 5648).
    • (1993) J. Chem. Phys. , vol.98 , pp. 5648
    • Becke, A.D.1
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    • Doctoral Dissertation, Indiana University
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    • Proton Affinity Evaluation
    • Mallard, W. G., Lindstrom, P. J., Eds.; March National Institute of Standards and Technology, Gaithersburg, MO, 20899
    • (a) Hunter, E. P.; Lias, S. G. Proton Affinity Evaluation. In NIST Chemistry Webbook, NIST Standard Reference Database Number 69; Mallard, W. G., Lindstrom, P. J., Eds.; March 1998, National Institute of Standards and Technology, Gaithersburg, MO, 20899 (http://webbook.nist-.gov).
    • (1998) NIST Chemistry Webbook, NIST Standard Reference Database Number 69
    • Hunter, E.P.1    Lias, S.G.2
  • 45
    • 0001159077 scopus 로고    scopus 로고
    • Considering the limitations of UMP2 method usage, strict interpretation of these results may be misleading. For a discussion of the use of UMP methods on diradicals see also Jarzecki, A. A.; Davidson, E. R. J. Phys. Chem. A 1998, 102, 4742.
    • (1998) J. Phys. Chem. A , vol.102 , pp. 4742
    • Jarzecki, A.A.1    Davidson, E.R.2
  • 50
  • 52
    • 0011577887 scopus 로고    scopus 로고
    • note
    • For a α-lactone ring opening similar to TS2 see ref 24, Table 6, p 6420. The cited C-C distance is 1.506 Å vs 1.500 Å in the structure optimized here, at the MP2/6-31G* level.
  • 53
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    • note
    • 14
  • 54
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    • note
    • Despite much effort, no TS7-like structure was found at higher levels, suggesting that TS7 may be an artifact due to the limitations of the HF theory used.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.