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A cautionary note is in order here, since new accurate experimental results regarding the reaction of 2-(1-adamantylethynyl)-pyrimidine5- carbaldehyde, published by Gehring et al. while ref. [12] was in press, could lead to a re-evaluation of the nature of the resting state in the Soai reaction as a function of substrate, temperature, and other experimental conditions: M. Busch, M. Schlageter, D. Weingand, T. Gehring
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A cautionary note is in order here, since new accurate experimental results regarding the reaction of 2-(1-adamantylethynyl)-pyrimidine5- carbaldehyde, published by Gehring et al. while ref. [12] was in press, could lead to a re-evaluation of the nature of the resting state in the Soai reaction as a function of substrate, temperature, and other experimental conditions: M. Busch, M. Schlageter, D. Weingand, T. Gehring, Chem. Eur. J. 2009, 15, 8251-8258.
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The M05-2X functional implicitly accounts for "medium-range" electron correlation because of the way in which it is parametrized. This is sufficient to describe the dispersion interactions within many complexes, apart from hydrogen-bonded systems, in which much of the dispersion interaction is "long-range" (>5 Å). E. G. Hohenstein, S. T. Chill, C. D. Sherrill
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The M05-2X functional implicitly accounts for "medium-range" electron correlation because of the way in which it is parametrized. This is sufficient to describe the dispersion interactions within many complexes, apart from hydrogen-bonded systems, in which much of the dispersion interaction is "long-range" (>5 Å). E. G. Hohenstein, S. T. Chill, C. D. Sherrill, J. Chem. Theory Comput. 2008, 4, 19962000.
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Computational details, optimized geometries and energies obtained with the program. Gaussian 03 are reported in the Supporting Information
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a) Computational details, optimized geometries and energies obtained with the program. Gaussian 03 are reported in the Supporting Information;
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Barone, V.14
Mennucci, B.15
Cossi, M.16
Scalmani, G.17
Rega, N.18
Petersson, G.A.19
Nakatsuji, H.20
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Nakajima, T.27
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Dapprich, S.52
Daniels, A.D.53
Strain, M.C.54
Farkas, O.55
Malick, D.K.56
Rabuck, A.D.57
Raghavachari, K.58
Foresman, J.B.59
Ortiz, J.V.60
Cui, Q.61
Baboul, A.G.62
Clifford, S.63
Cioslowski, J.64
Stefanov, B.B.65
Liu, G.66
Liashenko, A.67
Piskorz, P.68
Komaromi, I.69
Martin, R.L.70
Fox, D.J.71
Keith, T.72
Al-Laham, M.A.73
Peng, C.Y.74
Nanayakkara, A.75
Challacombe, M.76
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Johnson, B.78
Chen, W.79
Wong, M.W.80
Gonzalez, C.81
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more..
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This conclusion can be deduced by the observation of a secondorder dependency of the reaction rate on the aldehyde concentration coupled with the observation of a relatively low free energy of activation
-
This conclusion can be deduced by the observation of a secondorder dependency of the reaction rate on the aldehyde concentration coupled with the observation of a relatively low free energy of activation.
-
-
-
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74
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77649209789
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The B3LYP functional, systematically underestimates reaction barrier heights, and is known to be inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction and aromatic-aromatic stacking. See reference [14], and references therein
-
The B3LYP functional, systematically underestimates reaction barrier heights, and is known to be inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction and aromatic-aromatic stacking. See reference [14], and references therein.
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75
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84961980477
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77649195076
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[I0]
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[I0]
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77
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77649211052
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[10] In the light of the present results, this factor, although significant, cannot be considered the dominant one
-
[10] In the light of the present results, this factor, although significant, cannot be considered the dominant one.
-
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78
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77649213438
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[10]we erroneously considered evolution of the complex 6-R,anti-S,anti-P (Table 2, entry 10) as the most important catalytic cycle of the heterochiral dimer. Moreover, we did not succeed in locating the TS (6-R,anti-R,syn-P7-R,anti-RS) at the HF/ S3-21Gd level of theory
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[10]we erroneously considered evolution of the complex 6-R,anti-S,anti-P (Table 2, entry 10) as the most important catalytic cycle of the heterochiral dimer. Moreover, we did not succeed in locating the TS (6-R,anti-R,syn-P7-R,anti-RS) at the HF/ S3-21Gd level of theory.
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