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23
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34247546339
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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.
-
-
-
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24
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34247497894
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11
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11
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25
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4243943295
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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.
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0033559452
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-
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.
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-
-
-
31
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0033532866
-
-
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
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34247485111
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1965, 30, 728;
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34
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34247511740
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1966, 31, 1694.
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Salahub, D.R.4
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39
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34247465272
-
-
2 extruded from 1 by LFP.
-
2 extruded from 1 by LFP.
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-
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40
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33845278072
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Jackson, J. E.; Soundararajan, N.; Plate, M. S.; Liu, M. T. H. J. Am. Chem. Soc. 1988, 110, 5595.
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-
47
-
-
34247545381
-
-
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
-
-
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
-
-
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
-
-
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)
-
-
-
-
51
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43949151212
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Bearpark, M. J.; Robb, M. A.; Schlegel, H. B. Chem. Phys. Lett. 1994, 223, 269.
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56
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-
34247531627
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-
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
-
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34247547137
-
-
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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-
-
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