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Volumn 129, Issue 16, 2007, Pages 5167-5174

The synthesis of dichlorodiazirine and the generation of dichlorocarbene: Spectroscopy and structure of dichlorocarbene ylides

Author keywords

[No Author keywords available]

Indexed keywords

DICHLOROCARBENE; DICHLORODIAZIRINE; LASER FLASH PHOTOLYSIS (LFP); YLIDES;

EID: 34247549649     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja068727w     Document Type: Article
Times cited : (33)

References (58)
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    • and references therein
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  • 20
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    • Liu, M. T. H, Ed, CRC Press: Boca Raton, FL, Vols
    • Liu, M. T. H., Ed. Chemistry of Diazirines: CRC Press: Boca Raton, FL, 1987; Vols. I and II.
    • (1987) Chemistry of Diazirines , vol.I and II
  • 23
    • 34247546339 scopus 로고    scopus 로고
    • The chloride reagent mixture was preheated, dried, and liquified by heating to 80-85 °C under vacuum for 5 h.
    • The chloride reagent mixture was preheated, dried, and liquified by heating to 80-85 °C under vacuum for 5 h.
  • 24
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    • 11
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  • 29
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    • Frisch, M. J.; et al. Gaussian 03, revision B.03: Gaussian, Inc.: Pittsburgh. PA, 2003. See Supporting Information for the complete reference to Gaussian 03.
    • Frisch, M. J.; et al. Gaussian 03, revision B.03: Gaussian, Inc.: Pittsburgh. PA, 2003. See Supporting Information for the complete reference to Gaussian 03.
  • 30
    • 0033559452 scopus 로고    scopus 로고
    • Pliego, R. J., Jr.; De Almeida, W. B. Phys. Chem. Chem. Phys. 1999, 1, 1031 report an exothermicity of ΔH = -35.5 kcal/mol for this reaction on the basis of MP4/6-311G(2df,p)//MP2/6-31G* calculations.
    • Pliego, R. J., Jr.; De Almeida, W. B. Phys. Chem. Chem. Phys. 1999, 1, 1031 report an exothermicity of ΔH = -35.5 kcal/mol for this reaction on the basis of MP4/6-311G(2df,p)//MP2/6-31G* calculations.
  • 31
    • 0033532866 scopus 로고    scopus 로고
    • 2-thioanisole complexes were found to be 7-8 kcal/mol higher in energy than ylide 21 and, hence, are not energetically competitive.
    • 2-thioanisole complexes were found to be 7-8 kcal/mol higher in energy than ylide 21 and, hence, are not energetically competitive.
  • 33
    • 34247485111 scopus 로고
    • 1965, 30, 728;
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  • 39
    • 34247465272 scopus 로고    scopus 로고
    • 2 extruded from 1 by LFP.
    • 2 extruded from 1 by LFP.
  • 47
    • 34247545381 scopus 로고    scopus 로고
    • 2C· ··OO distance of about 2.0 Å leads from the weakly bound complex to the triplet carbonyl oxide. These stationary points are not present when the PBEPBE functionals are applied in the calculations. See the Supporting Information for additional structural and energetic details.
    • 2C· ··OO distance of about 2.0 Å leads from the weakly bound complex to the triplet carbonyl oxide. These stationary points are not present when the PBEPBE functionals are applied in the calculations. See the Supporting Information for additional structural and energetic details.
  • 48
    • 34247526138 scopus 로고    scopus 로고
    • A second triplet conformer, in which the pyramidalization at C is opposite, has a relative free energy 1.6 kcal/mol higher; the activation free energy barrier is 2.3 kcal/mol relative to that of 22T.
    • A second triplet conformer, in which the pyramidalization at C is opposite, has a relative free energy 1.6 kcal/mol higher; the activation free energy barrier is 2.3 kcal/mol relative to that of 22T.
  • 49
    • 34247497443 scopus 로고    scopus 로고
    • The transition computed in 22S is thus analogous to the weak n - π* absorptions exhibited by simple aldehydes and ketones.
    • The transition computed in 22S is thus analogous to the weak n - π* absorptions exhibited by simple aldehydes and ketones.
  • 50
    • 34247518866 scopus 로고    scopus 로고
    • Additional excitations are computed at 425.2 nm (f ≈ 0.0003) and at 356.2 nm (f ≈ 0.005). A near-infrared transition with no intensity is also predicted at λ= 1217 nm (f = 0.0000)
    • Additional excitations are computed at 425.2 nm (f ≈ 0.0003) and at 356.2 nm (f ≈ 0.005). A near-infrared transition with no intensity is also predicted at λ= 1217 nm (f = 0.0000)
  • 56
    • 34247531627 scopus 로고    scopus 로고
    • Using PBEPBE/6-3 11+g(d) derived energies (ΔE, 28.4 kcal/mol, λ, 23.0 kcal/mol) and HSO, 10.4 cm -1, we obtain klSC ≈ » 3.1 × 10 9 s-1 at T, 298 K
    • -1 at T = 298 K.
  • 57
    • 34247547137 scopus 로고    scopus 로고
    • This assignment should still be regarded as provisional. Although the 465 nm absorption clearly results from the reaction of CCl2 with oxygen, and computational studies provide for an extremely rapid formation of 22, we are unable to quench the absorbing species with TME, acetaldehyde, or tris(trimethylsilyl)silane, nor do we observe the formation of other UV active species (over 10 μs) as the 465 nm species decays
    • 2 with oxygen, and computational studies provide for an extremely rapid formation of 22, we are unable to quench the absorbing species with TME, acetaldehyde, or tris(trimethylsilyl)silane, nor do we observe the formation of other UV active species (over 10 μs) as the 465 nm species decays.


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