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It is possible to compute the difference in the free energies of activation for the two TSs at the B3LYP/6-31G* level, using expressions for the partition functions based on the rigid rotor/harmonic oscillator approximation, and this yields a difference of 2.03 kcal/mol. This value is not necessarily a closer approximation to the true difference in free energies of activation than is the difference in the energies of activation, given the errors involved in applying gas-phase rigid rotor/harmonic oscillator expressions to the reaction in solution, but it is satisfying to note ΔΔG‡ is similar to ΔΔE ‡
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For previous examples of this error cancellation in prediction of selectivity for complex systems, see
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In a recent computational study of enantioselectivity in hydrogenation of acetophenone by (SXylBINAP)RuH2(S,S-dpen),45 a different explanation has been given for the selectivity. The hydrogen transfer TSs located in this study are similar to those obtained here. The authors have also located weak hydrogen-bonded complexes between the dihydride catalyst and the ketone, similar in geometry to the intermediate B shown in Figure 2. As discussed above, such minima are likely to disappear in the presence of solvent and when taking entropic factors into account, so should not play an important role in the mechanism. However, in the case of the ax-out approach only, the authors located a second stable intermediate in which me ketone has moved closer to the transferring hydride and suggest that the presence of this stable species helps to explain the selectivity. No such minimum has been found in the present case, perhaps because the less bulky BINAP ligand was modeled ins
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45 a different explanation has been given for the selectivity. The hydrogen transfer TSs located in this study are similar to those obtained here. The authors have also located weak hydrogen-bonded complexes between the dihydride catalyst and the ketone, similar in geometry to the intermediate B shown in Figure 2. As discussed above, such minima are likely to disappear in the presence of solvent and when taking entropic factors into account, so should not play an important role in the mechanism. However, in the case of the ax-out approach only, the authors located a second stable intermediate in which me ketone has moved closer to the transferring hydride and suggest that the presence of this stable species helps to explain the selectivity. No such minimum has been found in the present case, perhaps because the less bulky BINAP ligand was modeled instead of XylBINAP. Since BINAP gives a similar pattern of stereoselectivity to XylBINAP, it is unlikely that any major effect is present with the latter ligand that is absent with BINAP. The appearance of the energy plot in ref 41 (Figure 2) suggests a conformational change, perhaps in the bulky xylyl sidechains, upon approach of the ketone. Such a change is unlikely to be rate-determining since it can also occur before the ketone binds.
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French, S. A.; Di Tommaso, D.; Zanotti-Gerosa, A.; Hancock, F.; Catlow, C. R. A. Chem. Commun. 2007, 2381-2383.
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Di Tommaso, D.2
Zanotti-Gerosa, A.3
Hancock, F.4
Catlow, C.R.A.5
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See for example
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(a) See for example: Jing, Q.; Zhang, X.; Sun, J.; Ding, K. Adv. Synth. Catal. 2005, 347, 1193-1197.
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Adv. Synth. Catal
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Ding, K.4
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(b) Jing, Q.; Sandoval, C. A.; Wang, Z.; Ding, K. Eur. J. Org. Chem. 2006, 3606-3616.
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(2006)
Eur. J. Org. Chem
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Wang, Z.3
Ding, K.4
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(c) Xia, Y. Q.; Tang, Y. Y.; Liang, Z. M.; Yu, C. B.; Zhou, X. G.; Li, R. X.; Li, X. J. J. Mol. Catal. A: Chem. 2005, 240, 132-138.
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Xia, Y.Q.1
Tang, Y.Y.2
Liang, Z.M.3
Yu, C.B.4
Zhou, X.G.5
Li, R.X.6
Li, X.J.7
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In fact, the prediction in our earlier work (ref 16) that hydrogen splitting was turnover limiting was made before experimental evidence for this became available
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In fact, the prediction in our earlier work (ref 16) that hydrogen splitting was turnover limiting was made before experimental evidence for this became available.
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