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In contrast to the LG being an alkyl group, phenyl group, or hydrogen
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In contrast to the LG being an alkyl group, phenyl group, or hydrogen.
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10
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0003429028
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(a) Bernasconi, C. F.; Ketner, R. J.; Ragains, M. L.; Chen, X.; Rappoport, Z. J. Am. Chem. Soc. 2001, 123, 2155.
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(c) Bernasconi, C. F.; Ketner, R. J.; Chen, X.; Rappoport, Z. J. Am. Chem. Soc. 1998, 120, 7461.
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(e) Bernasconi, C. F.; Ketner, R. J.; Chen, X.; Rappoport, Z. ARKIVOK 2002, xii, 161.
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84962403816
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The intrinsic barrier of a reaction refers to the barrier in the absence of a thermodynamic driving force.8b
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8b
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27
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33947088922
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Yokoyama, Y.; Ohashi, Y. Bull. Chem. Soc. Jpn. 1999, 72, 2183. See also references cited in the papers above.
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(j) Yokoyama, Y.; Ohashi, Y. Bull. Chem. Soc. Jpn. 1999, 72, 2183. See also references cited in the papers above.
-
-
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43
-
-
84962417566
-
-
Equation 2 includes only the 2-fold component of a more general equation suggested in ref 10b
-
(b) Equation 2 includes only the 2-fold component of a more general equation suggested in ref 10b.
-
-
-
-
44
-
-
84962417569
-
-
-).
-
-).
-
-
-
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45
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0348125932
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(a) Lathan, W. A.; Radom, L.; Hehre, W. J.; Pople, J. A., J. Am. Chem. Soc. 1973, 95, 699.
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Lathan, W.A.1
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47
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84962445215
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Gaussian 98 (revision A.11) and Gaussian 03 (revision B.05): M. J. Frisch, et al., Gaussian, Inc., Pittsburgh, PA, 2001. The complete reference is given in the Supporting Information.
-
Gaussian 98 (revision A.11) and Gaussian 03 (revision B.05): M. J. Frisch, et al., Gaussian, Inc., Pittsburgh, PA, 2001. The complete reference is given in the Supporting Information.
-
-
-
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50
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33751157732
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84962355903
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NBO, v 5.0: Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F., Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001; http://www.chem.wisc.edu/_nbo5.
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(a) NBO, v 5.0: Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F., Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001; http://www.chem.wisc.edu/_nbo5.
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84946893847
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61
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84962358732
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To test the reliability of this method for calculating pK a values and stabilization trends in our systems, we calculated pKa differences (ΔpKa) in water solution between HA and HB according to HA, B- → HB, A, ΔpKa, ΔGgas, ΔGsolv)/2.3RT (T, 298 K).21b ΔpKa(CF3CH2OH-CH3OH, 5.3 (experimental -3.1),21c,d ΔpKa(Meldrum acid (19b, CF3CH2OH, 6.2 (experimental -7.6),21c,d and ΔpKa(Meldrum acid (19b, CH3OH, 11.6 (experimental -10.7).21c,d Part of the computational error results from errors in the computated ΔGgas. However, the trends are well reproduced. 21e
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21e
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62
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1642502285
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67
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84962417519
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-
α = -69.3° and -65.9°.
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α = -69.3° and -65.9°.
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-
-
-
68
-
-
84962417520
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-
β bonds of 1.105 and 1.426 Å, respectively.
-
β bonds of 1.105 and 1.426 Å, respectively.
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-
-
-
70
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84962407236
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-
The p(X) → σ*(Cβ-X) NBO energy differences are (eV) 12.1 (2p(CH3O) → σ*(C β-SCH3, < 14.5 (3p(CH3S) → σ*(Cβ-OCH3, 15.8 (2p(OCH3) → σ*(Cβ-OCH2CF3, < 16.9 (2p(CF3CH2O) → σ*(C β-OCH3, and 12.9 (2p(OCH2CF3) → σ*(Cβ-SCH3, < 14.2 (3p(SCH3) → σ*Cβ-OCH 2CF3
-
3)).
-
-
-
-
71
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84962387903
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-
A significantly smaller stabilizing effect is caused by the interaction between the lone pairs on O and S and the σ*C-CH2 , orbital. Its contribution to the stability of 7b and 7c is calculated to be ca. 2.0 kcal/mol
-
-) orbital. Its contribution to the stability of 7b and 7c is calculated to be ca. 2.0 kcal/mol.
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-
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72
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84962387900
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21b,c
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21b,c
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84962417551
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In all reactions where the substituents are being separated from each other, we have to consider the release of steric repulsion between the geminal X and Z substituents
-
(a) In all reactions where the substituents are being separated from each other, we have to consider the release of steric repulsion between the geminal X and Z substituents.
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76
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84962417557
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7a,d
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7a,d
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84962381925
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